Use of amino or hydrazino peroxides in preparing and curing polymers

ABSTRACT

This invention relates to novel reactive amino or hydrazino peroxides (hereinafter generally referred to as &#34;AHP&#39;s&#34;) and derivatives all having a Structure A: ##STR1## in which the definitions of P, R11, R22, X, Q and x, y and z are given in the Summary Of The Invention section, for example, 4,4-di-(t-butylperoxy)pentanohydrazide (I-1), and the use of these novel compounds in curing unsaturated polyester resins, in initiating polymerization of ethylenically unsaturated monomers, for modifying rheology, for crosslinking and curing olefin polymers and elastomers, for producing novel graft and block copolymers, and for producing novel polymers with covalently bound performance additive functions.

This is a divisional of application Ser. No. 08/287,692 filed on Aug. 9,1994, now U.S. Pat. No. 5,399,630 which is a divisional of applicationSer. No. 08/169,808 filed on Dec. 17, 1993 now U.S. Pat. No. 5,360,867which is a divisional of application Ser. No. 07/565,822 filed Aug. 10,1990 now U.S. Pat. No. 5,272,219 which is a divisional of applicationSer. No. 07/233,643 filed Aug. 18, 1988 now U.S. Pat. No. 4,956,416.

BACKGROUND OF THE INVENTION

1. Field Of The Invention

This invention relates to novel reactive amino or hydrazino peroxides(hereinafter generally referred to as "AHP's") and derivatives allhaving a Structure A: ##STR2## in which the definitions of P, R11, R22,X, Q and x, y and z are given in the Summary Of The Invention section,for example, 4,4-di-(t-butylperoxy)pentanohydrazide (I-1), and the useof these novel compounds in curing unsaturated polyester resins, ininitiating polymerization of ethylenically unsaturated monomers, formodifying rheology, for crosslinking and curing olefin polymers andelastomers, for producing novel graft and block copolymers, and forproducing novel polymers with covalently bound performance additivefunctions.

2. Description of the Prior Art

The novel reactive amino or hydrazino peroxides of the instant inventionpossess reactive amino or hydrazino functional groups. Peroxides withother types of reactive functional groups are known in the literatureand several are sold commercially. Commercially produced peroxides withreactive functional groups include succinic acid peroxide (carboxygroup) and OO-t-butyl O-hydrogen monoperoxymaleate (carboxy group). Morerecently, 3-hydroxy-1,1-dimethylbutyl peroxy-2-ethylhexanoate (hydroxygroup) and 3-hydroxy-1,1-dimethylbutyl peroxyneoheptanoate (hydroxygroup) have been offered commercially. Such initiators enable polymerproducers to enhance the utility and value of polymers by allowing themto `put` the reactive groups onto polymers by means of free-radicalpolymerization of ethylenically unsaturated monomers or by means ofgrafting reactions using these reactive peroxide initiators.

Other reactive initiators are disclosed in the literature. U.S. Pat. No.3,236,872 discloses hydroxy-peroxides. U.S. Pat. No. 3,991,085 disclosesepoxy-peroxides. U.S. Pat. No. 3,660,468 discloses peroxides havingreactive carboxy groups, particularly mono-peresters of α,αdisubstitutedmalonic acid. U.S. Pat. No. 3,671,651 discloses peroxides havingreactive acylating groups, such as acyl halide groups, haloformategroups or anhydride groups. U.S. Pat. No. 3,952,041 discloses peroxideswith reactive acid chloride groups.

The prior art reactive functional peroxides are not as completely orcleanly reactive with co-reactive anhydride containing compounds andpolymers as are the reactive amino and hydrazino peroxides of StructureA. Unlike hydroxy compounds, amino and hydrazino compounds form verystable reaction products with cyclic anhydrides, i.e., amic acids andimides. In contrast, hydroxy compounds react to form carboxy esters thatare unstable at the elevated temperatures at which imides are verystable. It is very well known that the cyclic imide structure is verystable thermally. Indeed, polyimides belong to a class of polymers thatexhibit extremely high thermal stability owing to the cyclic imidelinkage. Because of this enhanced thermal stability, polyimides areemployed in very high temperature applications.

Some peroxides possessing amino groups are known. E. G. E. Hawkins,Angewandte Chemie, Vol. 12, pp. 783-793 (1973) disclosesα-aminoperoxides where the amino group is attached to the same carbonatom as the peroxide group, but does not include α-peroxyhydrazines orα-peroxyazo compounds. For example, this reference indicates that1-hydroperoxycyclohexylamine is known but is relatively unstable at roomtemperature. Reaction of 1-hydroperoxyalkylamines with ketones andaldehydes yield 1,2,4-dioxazolidines which are cyclic peroxyamines. Such1,2,4-dioxazolidines have only one --NH bond, hence, they cannot be usedto synthesize stable peroxyimides. The terminal --NH₂ groups of theAHP's of Structure A of the present invention are distanced from theperoxide functional group of the AHP's, hence, the AHP's areconsiderably more stable and more useful than 1-peroxyalkylamines or the1,2,4-dioxazolidines.

Diperoxyketals and diperoxyketal salts derived from2,2,6,6-tetraalkyl-4-piperidinone and1,2,2,6,6-pentaalkyl-4-piperidinone have been disclosed in CanadianPatent 1,194,477, issued Oct. 1, 1985. However, the amino function ofthese compounds is quite hindered and is quite non-reactive with cyclicanhydrides.

The derivatives of the AHP's of the instant invention within Structure Aare novel. Amino peroxides are disclosed in the previously cited Hawkinsarticle and in U.S. Pat. No. 4,180,518. The Hawkins article disclosesN-acyl derivatives of 1-peroxyalkylamines- U.S. Pat. No. 4,180,518discloses carbamate derivatives of dialkyl peroxides,monoperoxycarbonates and peroxycarbamates,

U.S. Pat. No. 4,072,810 -discloses coupled peroxides but does notinclude the coupled peroxides of the present invention. The coupledperoxides of the present invention, derived from the AHP's, are coupledwith either a urea functional group or a carbazate functional group.

U.S. Pat. No. 3,706,818 discloses polyperoxy sequential radicalinitiators (sequential peroxides), but not the sequential peroxides ofthe present invention which are derived from the AHP's and withinStructure A. The sequential peroxides of the present invention arecoupled with a carbazate functional group.

With respect to peroxy UV stabilizers derived from the AHP's, U.S. Pat.No. 4,129,586 discloses (column 22, lines 42 through 55) that thepatented free radical initiators containing UV stabilizer groups can beprepared by a variety of techniques including reacting a UV stabilizercontaining an acylating functional group with an azo or peroxidecontaining a reactive --OH, --SH or --NH group, among other techniques.

The peroxy UV stabilizers of the present invention, i.e., those derivedfrom the novel AHP's of this invention, are prepared by reacting a UVstabilizer having an acylating function with a peroxide having areactive hydrazide group.

With respect to the novel polymeric derivatives of the AHP's of thisinvention, the inventor of the instant invention is unaware of anypublished art pertaining to peroxy polymers having peroxy groupscovalently bound to the polymer via amic acid or imide moieties.

There is a need in the polymer industry for reactive functionalizedinitiators (peroxides and azos) which can be used to produce reactive,functionalized polymers or peroxy-polymers by various means such asfree-radical polymerization of ethylenically unsaturated monomers,grafting onto polymers, chain termination of condensation polymers,reaction with co-functionalized polymers, etc. When the initiator groupof the functionalized initiator decomposes in these processes, polymerswith functional groups (i.e., at chain ends or pendant from the chains)are produced. Such polymers can be chain extended to produce desirablehigh performance polymers. This technique is the basis for the highsolids acrylic coatings business in which hydroxy-containing lowmolecular weight acrylic copolymers are chain extended and/or crosslinked with co-reactive compounds after being applied in automotivecoatings applications.

When a reactive functional initiator is used to chain terminatecondensation polymers or to react with co-reactive polymers, polymerswith pendant initiator groups and/or initiator end groups are produced.These peroxy-polymers can then be used to produce block or graftcopolymers that can be used in compatibilizing polymer blends and alloysproduced from incompatible polymers.

Because of this there is a need for reactive functional initiators thatare reactive with commercially available and inexpensive co-reactivepolymers. The co-reactive polymers that are available include thosewhich have hydroxy groups, such as poly(vinyl alcohol) and acryliccopolymers derived from hydroxyalkyl acrylates and methacrylates; thosewhich have carboxy groups, such as maleic acid, fumaric acid, acrylicacid and methacrylic acid copolymers; and anhydride copolymers, such asthose derived from maleic anhydride and acrylic acid anhydride.

Reactive functionalized initiators that are co-reactive with hydroxypolymers are those having acid halide, haloformate or anhydride groups.In general, the reaction requires the presence of a base, hence, thereactions have to be done in a solvent rather in more convenient polymermixing equipment such as an extruder.

Reactions between polymers with carboxy groups and initiators withco-reactive groups are sluggish unless the carboxy groups are initiallyconverted to acid halide groups. The latter reaction has to be done insolution as would the subsequent reaction between the polymer with acidhalide groups and the initiator with co-reactive groups (e.g., hydroxygroups). Polymer solution reactions are inconvenient and are expensiveto run.

Reactions between polymers with anhydride groups and co-reactiveinitiators appear to have potential for producing polymeric peroxideseconomically. Making these polymeric substrates even more attractive isthe fact that numerous anhydride copolymers are commercially availableas low cost resins. Available are styrene/maleic anhydride(MA)copolymers, ethylene/MA copolymers, octadecene/MA copolymers, alkylvinyl ether/MA copolymers, grafted MA modified polyolefins and others.However, the reaction between a hydroxy containing peroxide and a MAcopolymer is expected to give a poly(carboxy ester) with pendantperoxide functions. At elevated temperatures the peroxy polymer isexpected to decompose to yield the MA copolymer and the hydroxycontaining peroxide. In comparison, the AHP's of the instant inventionreact with MA copolymers to initially form poly(peroxy amic acid)polymers which on heating to elevated temperatures further react, withelimination of water, to give poly(peroxyimide) polymers with thermallystable imide groups.

SUMMARY OF THE INVENTION

The present invention concerns a peroxide compound having reactive aminoor hydrazino functional groups capable of forming a stable amic acid orcyclic imide compound in a reaction with a cyclic anhydride, where thereare at least 2 carbon atoms between the reactive amino or hydrazinofunctional group and the peroxide group. As used herein, "peroxidegroup" means the --OO-- group.

The present invention also relates to amino or hydrazino peroxides(AHP's) and derivatives of Structure A: ##STR3## where x is 0 or 1, y is1 or 2 and z is 1 to 3, with the further provisos that when y is 2, zcan only be 1 and when z is 2 or 3, y can only be 1, and

(I) when y is 1 and z is 1,

P is a peroxide-containing mono-radical having a structure: ##STR4##where w is 1 or 2;

R is a substituted or unsubstituted t-alkyl radical of 4 to 12 carbons,a substituted or unsubstituted t-aralkyl radical of 9 to 13 carbons, at-cycloalkyl radical of 5 to 12 carbons or a substituted orunsubstituted t-alkynyl radical of 5 to 10 carbons;

R1 is a substituted or unsubstituted, branched or unbranched, alkylradical of 1 to 13 carbons, a substituted or unsubstituted cycloalkylradical of 5 to 10 carbons, a substituted or unsubstituted, branched orunbranched, aralkyl radical of 7 to 11 carbons, or a substituted orunsubstituted aryl radical of 6 to 10 carbons;

R1' is a substituted or unsubstituted, branched or unbranched, alkylradical of 1 to 13 carbons, a substituted or unsubstituted cycloalkylradical of 5 to 10 carbons, or a substituted or unsubstituted, branchedor unbranched, aralkyl radical of 7 to 11 carbons;

R2' and R3 are the same or different and are substituted orunsubstituted alkyl radicals of 1 to 4 carbons;

the substituents for R, R1, R1', R2 and R3 being alkyl radicals of 1 to4 carbons, chloro or bromo;

R4 is hydrogen, a substituted or unsubstituted alkyl radical of 1 to 10carbons or a substituted or unsubstituted aryl radical of 6 to 10carbons, the R4 substituents being one or more alkyl radicals of 1 to 8carbons, chloro, bromo or carboxy;

T is nothing or --O--;

R11 is a substituted or unsubstituted alkylene diradical of 2 to 8carbons or a substituted or unsubstituted 1,2-, 1,3- or 1,4-phenylenediradical, the R11 substituents being alkyl radicals of 1 to 4 carbons,chloro or bromo;

X is nothing, ##STR5## R22 is nothing, a substituted or unsubstitutedalkylene diradical of 2 to 10 carbons or a substituted or unsubstituted1,2-, 1,3- or 1,4-phenylene diradical, the R22 substituents being alkylradicals of 1 to 3 carbons, chloro or bromo;

Q is a nitrogen-containing radical having a nitrogen-containingstructure (a), (b), (c), (d) or (e), or a recurring unit in a polymerhaving a structure (f) or (g): ##STR6## where R33 is a substituted orunsubstituted 1,2- or 1,3- alkylene diradical of 2 to 18 carbons, asubstituted or unsubstituted 1,2- or 1,3-alkenylene diradical of 2 to 18carbons, a substituted or unsubstituted 1,2-cycloalkylene diradical of 5to 6 carbons, a substituted or unsubstituted 1,2-cycloalkenylenediradical of 5 to 6 carbons, a substituted or unsubstituted1,2-bicycloalkylene diradical of 7 to 9 carbons, a substituted orunsubstituted 1,2-bicycloalkenylene diradical of 7 to 9 carbons, asubstituted or unsubstituted 1,2-phenylene diradical, a substituted orunsubstituted 1,2-naphthenylene diradical, a substituted orunsubstituted 2,3-naphthenylene diradical or a substituted orunsubstituted 1,8-naphthenylene diradical, the R33 substituents beingone or more alkyl radicals of 1 to 8 carbons, chloro, bromo, nitro,carboxy, alkoxy radicals of 1 to 8 carbons or alkoxycarbonyl radicals of2 to 9 carbons;

R33' is a substituted or unsubstituted 1,2-phenylene diradical, the R33'substituents being one or more alkyl radicals of 1 to 8 carbons, chloroor bromo;

A.sup.⊖ is chloride, bromide, sulfate, acid sulfate, phosphate, acidphosphate, p-methylphenylsulfonate, phenylsulfonate, methylsulfonate,phenylphosphonate, cyclohexylphosphonate or carboxylate from anycarboxylic acid;

R5 is hydrogen, a substituted or unsubstituted acyl radical of 1 to 18carbons, a substituted or unsubstituted alkenoyl radical of 3 to 10carbons, a perfluoroacyl radical of 2 to 18 carbons, a substituted orunsubstituted aroyl radical of 7 to 11 carbons, a substituted orunsubstituted cycloalkylcarbonyl radical of 6 to 13 carbons, asubstituted or unsubstituted cycloalkenylcarbonyl radical of 6 to 13carbons, a substituted or unsubstituted bicycloalkylcarbonyl radical of6 to 13 carbons, a substituted or unsubstituted alkoxycarbonyl radicalof 2 to 19 carbons, a substituted or unsubstituted alkenyloxycarbonylradical of 3 to 8 carbons, a substituted or unsubstitutedaryloxycarbonyl radical of 7 to 11 carbons, a substituted orunsubstituted cycloalkoxycarbonyl radical of 6 to 13 carbons, asubstituted or unsubstituted alkylaminocarbonyl radical of 2 to 19carbons, a substituted or unsubstituted alkenylaminocarbonyl radical of3 to 8 carbons, a substituted or unsubstituted arylaminocarbonyl radicalof 7 to 11 carbons, an alkylsulfonyl radical of 1 to 8 carbons, asubstituted or unsubstituted arylsulfonyl radical of 6 to 10 carbons, ora radical having a structure (h) , (i) , (j) , (k) or (1): ##STR7##where W is nothing, --NH--, ##STR8## Y is --NH--, --S--, --SO--, SO₂ or--O--; R6 is an alkyl radical of 1 to 18 carbons, an aryl radical of 6to 12 carbons or an aralkyl radical of 7 to 11 carbons;

R7 is H, an alkyl radical of 1 to 4 carbons, an acyl radical of 2 to 18carbons, an aroyl radical of 7 to 15 carbons, an alkoxycarbonyl radicalof 2 to 19 carbons or an aryloxycarbonyl radical of 7 to 15 carbons;

R44 is nothing or an alkylene diradical of 1 to 6 carbons, andpreferably, 1 to 3 carbons;

v is 0 or 1;

S_(b) is nothing or one or more of alkyl radicals of 1 to 4 carbons,lower alkoxy, chloro, bromo, cyano or nitro;

S_(b) ' is nothing or one or more of alkyl radicals of 1 to 4 carbons,t-butyl radicals, t-amyl radicals, t-octyl radicals, alpha-cumylradicals, alkoxy radicals of 1 to 4 carbons, chloro, bromo, cyano ornitro;

the R5 substituents being one or more alkyl radicals of 1 to 8 carbons,chloro, bromo, nitro, carboxyl, alkoxy radicals of 1 to 8 carbons oralkoxycarbonyl radicals of 2 to 9 carbons, with the proviso that whenR22 is nothing, the R5 substituents can additionally be at-alkylperoxycarbonyl radical of 5 to 9 carbons, at-alkylperoxycarbonyloxy radical of 5 to 9 carbons, or a t-alkylperoxyradical of 4 to 8 carbons;

R8 is a substituted or unsubstituted alkylidene diradical of 2 to 12carbons, a substituted or unsubstituted cycloalkylidene diradical of 5to 12 carbons, optionally possessing as one or more heteroatoms N, O orS in the cycloalkylidene chain, or a substituted or unsubstitutedbenzylidene diradical of 7 to 11 carbons, the R8 substituents being oneor more alkyl radicals of 1 to 8 carbons, chloro, bromo, carboxy ornitro;

the recurring unit in polymer structures (f) and (g) being,respectively: ##STR9## in which the recurring units (f) or (g) occur inthe polymer backbone or as pendant units or both,

where

Ri and Rii are the same or different and are hydrogen, an alkyl radicalof 1 to 6 carbons, a cycloalkyl radical of 5 to 7 carbons, phenyl,chloro or bromo;

t is 0 or 1; and

G shows the point of attachment of group Q to the residue of StructureA;

(II) when y is 1 and z is 2,

P is a peroxide-containing diradical having a structure: ##STR10## whereR55 is an alkylene diradical of 1 to 6 carbons, an alkynylene diradicalof 2 to 6 carbons, an alkadiynylene diradical of 4 to 8 carbons or a1,3- or 1,4-phenylene diradical; and

R11, X, R22, Q, R, R1, R2, R3 and x are the same as when y is 1 and z is1, with the proviso that Q cannot be the above-defined recurring unit(f) or (g) in a polymer;

(III) when y is 1 and z is 3,

P is a peroxide-containing tri-radical having a structure: ##STR11##where R11, X, R22, Q, R, R1, R2, R3 and x are the same as when y is 1and z is 1, with the proviso that Q cannot be the above-definedrecurring unit in a polymer; and

(IV) when z is 1 and y is 2,

P, R11 and X are the same as when y is 1 and z is 1;

R22 is nothing; and

Q is a nitrogen-containing diradical having a structure (m), (n) or (o):##STR12## where R5 ' is --SO₂ --, ##STR13## where R66 is nothing or adiradical having a structure:

    --R77--,

    --Y--R77--Y--,

    --R77--Z----R77--

or

    --Y--R77--Z--R77--Y--,

where

R77 is a substituted or unsubstituted alkylene diradical of 2 to 10carbons, optionally having one or more --O-- or --S-- heteroatoms in thealkylene chain, or a substituted or unsubstituted 1,2-, 1,3- or1,4-phenylene diradical, the R77 substituents being one or more alkylradicals of 1 to 8 carbons, chloro, bromo, carboxy, nitro or alkoxyradicals of i to 8 carbons;

Z is nothing or a substituted or unsubstituted alkylene diradical of 1to 8 carbons, or a diradical having a structure: ##STR14## where R9 andR9' are the same or different and are hydrogen or alkyl radicals of 1 to10 carbons, and R9 and R9' can be connected together to form acarbocyclic ring containing 5 to 12 carbons and having substituents ofone or more alkyl radicals of 1 to 4 carbons; and

R88 is a substituted or unsubstituted alkylene diradical of 2 to 10carbons, the R88 substituents being alkyl of 1 to 8 carbons, chloro,bromo, carboxy, alkoxy radicals of 1 to 8 carbons, alkoxycarbonylradicals of 2 to 8 carbons, acyloxycarbonyl radicals of 2 to 8 carbonsor nitro.

Other aspects of the present invention include:

A. Novel processes for curing an unsaturated polyester resin by reactingthe resin in the presence of an amount of an AHP of Structure A underconditions effective to cure the resin.

B. Novel processes for preparing novel polymeric peroxides of StructureA, where Q is a recurring unit having a structure ##STR15## in which theunits occur in the polymer backbone or as pendant units or both, and

where G shows the point of attachment of group Q to the residue ofStructure A,

by reacting an anhydride-containing copolymer with recurring units ofthe structure ##STR16## in which the units occur in the polymer backboneor as pendant units or both,

with novel non-polymeric AHP's of Structure A, where Q is --NH₂, wherethe reaction occurs in solution or in a polymer melt under conditionseffective for preparing the novel polymeric peroxides.

C. Novel processes for initiating the polymerization of ethylenicallyunsaturated monomers by reacting the monomers with an initiating amountof an AHP of Structure A and under conditions effective to initiatepolymerization of the monomers. Typical monomers include, for example,styrene, ethylene and vinyl chloride.

D. Novel processes for curing elastomeric resins by reacting the resinsin the presence of an initiating amount of an AHP of Structure A andunder conditions effective to cure the elastomeric resins. Typicalelastomeric resins include, for example, ethylene-propylene copolymers(EPR), ethylene-propylene-diene terpolymers (EPDM), and butadienerubbers.

E. Novel processes for modifying polymers by varying the molecularweight and modifying the molecular weight distribution of the polymers,namely, polypropylene (PP), or copolymers comprising more than 50% byweight of polypropylene, by reacting the polymer or copolymer in thepresence of an amount of an AHP of Structure A and under conditionseffective to modify the polymer or copolymer.

F. Novel processes for crosslinking olefin polymers by reacting thepolymers in the presence of an amount of an AHP of Structure A and underconditions effective to crosslink the polymers. Typical olefin polymersinclude, for example, low density polyethylene (LDPE), linear lowdensity polyethylene (LLDPE) and high density polyethylene (HDPE)

G. Novel processes for preparing polymers with covalently boundperformance additive functional groups by reacting with the polymers anAHP of Structure A having at least one performance additive functionalgroup under conditions effective to covalently bond the AHP to thepolymers in a manner to enhance the performance of the polymers.Preferably, the performance additive functional groups are groups (h),(i), (j), (k) or (l) of Structure A as set forth above.

H. Novel processes for preparing novel block or graft copolymers usefulfor compatibilizing blends and alloys of two or more polymers byreacting with the polymers or monomers used to form the block or graftcopolymers a polymeric peroxide of Structure A under conditionseffective to form the block or graft copolymers.

The amounts of reactants and the reaction conditions of the abovesummarized processes, such as temperature, time, pressure, additionrates, etc., would be well known to those skilled in the art based onthe disclosure herein, or would be readily discernible therefrom withoutundo experimentation.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preparation of theNovel Amino or Hydrazino Peroxides (AHP's) of Structure A

Several synthesis processes are available for preparing the novel AHP'spossessing terminal amino groups.

One process is to react excess hydrazine or diamine with a peroxidepossessing an acid halide functional group, a haloformate functionalgroup, an acid anhydride functional group or an ester functional group.In the cases where excess hydrazine or a diamine is reacted with aperoxide possessing an acid halide functional group, a haloformatefunctional group or an acid anhydride functional group, the excesshydrazine or diamine acts as the base in the reaction. Alternately,another base can be used with the hydrazine or diamine, such astriethylamine, tributylamine, N,N-dimethylaniline, sodium hydroxide,sodium carbonate, sodium hydrogen carbonate, potassium hydroxide,potassium carbonate, potassium hydrogen carbonate, calcium hydroxide,barium hydroxide, calcium carbonate and trisodium phosphate, forexample.

Useful forms of hydrazine in these processes include anhydrous hydrazineas well as aqueous hydrazine compositions, e.g., 85% hydrazine hydrate(54.4% hydrazine). Useful diamines in these processes includeethylenediamine, 1,4-butylenediamine, hexamethylenediamine,1,4-phenylenediamine, 1,3-phenylenediamine and others.

Useful peroxides possessing acid halide functional groups, haloformatefunctional groups, acid anhydride functional groups and ester functionalgroups can be prepared by methods well known in the art and include, forexample, 2-(t-butylperoxycarbonyl)benzoyl chloride,3-(t-butylperoxycarbonyl)propionyl chloride,4-(t-amylperoxycarbonyl)butyryl chloride, 4,4-di-(t-butylperoxy)pentylchloroformate, 1,3-dimethyl-3-(t-butylperoxy)butyl chloroformate,3-methyl-3-(t-butylperoxy)butyl chloroformate,1,3-dimethyl-3-(t-amylperoxy)butyl chloroformate,1,3-dimethyl-3-(2-ethylhexanoylperoxy)butyl chloroformate,1,3-dimethyl-3-(neoheptanoylperoxy)butyl chloroformate,di-(1,1-dimethyl-3-chlorocarbonyloxybutyl) peroxide,di-(1,1-dimethyl-3-chlorocarbonyl-oxypropyl) peroxide,4,4-di-(t-butylperoxy)pentanoic acid anhydride, methyl3,3-di-(t-butylperoxy)butyrate, methyl 3,3-di-(t-amylperoxy)butyrate,n-butyl 3,3-di-(t-butylperoxy)butyrate, phenyl3,3-di-(t-butylperoxy)butyrate, methyl 4,4-di-(t-butylperoxy)pentanoate,ethyl 4,4-di-(t-butylperoxy)pentanoate, n-butyl4,4-di-(t-butylperoxy)pentanoate, phenyl4,4-di-(t-butylperoxy)pentanoate, t-butyl4,4-di-(t-butylperoxy)pentanoate,3-(methoxycarbonylmethyl)-3,5,7,7-tetramethyl-1,2,4-trioxacycloheptane,3-(2-ethoxycarbonylethyl)-3,5,7,7-tetramethyl-1,2,4-trioxacycloheptane,3-(methoxycarbonylmethyl)-3,6,6,9,9-pentamethyl-1,2,4,5-tetraoxacyclononaneand3-(2-ethoxycarbonylethyl)-3,6,6,9,9-pentamethyl-1,2,4,5-tetraoxacyclononane.

Another synthesis route to AHP's possessing terminal amino groupsinvolves using 1-(1-isocyanato-1-methylethyl)-4-isopropenylbenzene asthe starting material. Initially the latter reactant is reacted with analcohol, for example, methanol, to form O-methylN-(1-methyl-1-[4-isopropenylphenyl]ethyl) carbamate. Subsequently, thisintermediate is reacted with a hydroperoxide, for example, t-butylhydroperoxide, in the presence of an acid catalyst, such as anhydroushydrogen chloride, sulfuric acid and/or p-toluenesulfonic acid. Theresulting product, O-methylN-(1-methyl-1-[4-(1-methyl-1-[t-butylperoxy]ethyl)phenyl]ethyl)carbamate, is subsequently hydrolyzed in the presence of theabove-identified or other suitable, well known acid or base catalyst toyield the amino-peroxide,1-(1-amino-1-methylethyl)-4-(1-methyl-1-[t-butylperoxy]ethyl)benzene.

Non-limiting examples of the novel AHP's possessing a terminal aminogroup include the following:

AHP's With Terminal Amino Groups

4,4-Di-(t-butylperoxy)pentanohydrazide

4,4-Di-(t-amylperoxy)pentanohydrazide

3,3-Di-(t-butylperoxy)butanohydrazide

3-(1,4,4,6-Tetramethyl-2,3,7-trioxacycloheptyl)propionhydrazide

N-(2-Aminoethyl) 4,4-di-(t-butylperoxy)pentamide

1,3-Dimethyl-3-(t-butylperoxy)butyl carbazate

1,3-Dimethyl-3-(t-amylperoxy)butyl carbazate

1,3-Dimethyl-3-(2-ethylhexanoylperoxy)butyl carbazate

1,3-Dimethyl-3-(neoheptanoylperoxy)butyl carbazate

1,3-Dimethyl-3-(neodecanoylperoxy)butyl carbazate

4,4-Di-(t-butylperoxy)pentyl carbazate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-(2-aminoethyl) carbamate, alsoknown by the alternate name 1,3-dimethyl-3-(t-butylperoxy)butylN-(2-aminoethyl) carbamate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-(6-aminohexyl) carbamate

O-(1,3-Dimethyl-3-[2-ethylhexanoylperoxy]butyl) N-(2-aminoethyl)carbamate

O-(4,4-Di-[t-butylperoxy]pentyl) N-(2-aminoethyl) carbamate

1-(1-Amino-1-methylethyl)-4-(1-methyl-1-[t-butylperoxy]ethyl)benzene

1-(1-Amino-1-methylethyl)-3-(1-methyl-1-[t-butylperoxy]ethyl)benzene

Derivatives of AHP's Within Structure A

Novel derivatives of the above defined AHP's can be synthesized byreacting the AHP's with compounds that are reactive with the aminofunctional group of the AHP's. Bases useful in these reactions includethe bases listed above. Such reactive compounds include acid halides,chloroformates, carboxylic acid anhydrides, sulfonyl halides,isocyanates, ketones and aldehydes, alkylating agents, epoxides,acrylonitrile, methacrylonitrile and organic or mineral acids.

Reacting AHP's with acid halides, such as acetyl chloride, butyrylchloride, pivaloyl chloride, 2-ethylhexanoyl chloride, neodecanoylchloride, stearoyl chloride, acryloyl chloride, methacryloyl chloride,dodecanedioyl dichloride, adipoyl chloride, benzoyl chloride,2-methylbenzoyl chloride, 4-methylbenzoyl chloride,2-(methoxycarbonyl)benzoyl chloride, 2-(2-ethylhexoxycarbonyl)benzoylchloride, 2-naphthoyl chloride, phthaloyl chloride and terephthaloylchloride, results in the formation of acyl substituted amide, carbazateor hydrazide derivatives.

Reacting AHP's with chloroformates such as methyl chloroformate,isopropyl chloroformate, 2-ethylhexyl chloroformate, hexadecylchloroformate, 2-(acryloxyethyl) chloroformate, methacryloxypropylchloroformate, 2-phenoxyethyl chloroformate, ethylene glycolbischloroformate, diethylene glycol bischloroformate, phenylchloroformate, bisphenol A bischloroformate, results in the formation ofalkoxycarbonyl or aryloxycarbonyl substituted amide, carbazate orhydrazide derivatives.

Reacting AHP's with carboxylic acid anhydrides, such as aceticanhydride, maleic anhydride, itaconic anhydride, succinic anhydride,glutaric anhydride, 1-dodecene-succinic anhydride, phthalic anhydride,trimellitic anhydride, pyromellitic dianhydride and benzophenonedianhydride, results in the formation of acyl or carboxyacyl substitutedamide, carbazate or hydrazide derivatives or substituted imidederivatives.

Reacting AHP's with sulfonyl halides, such as p-methylphenylsulfonylchloride and methylsulfonyl chloride, results in the formation ofsulfonyl substituted amide, carbazate or hydrazide derivatives.

Reacting AHP's with isocyanates, such as phenyl isocyanate, methylisocyanate, hexamethylene diisocyanate, toluene diisocyanate,diphenylmethane diisocyanate and isophorone diisocyanate, results in theformation of alkylaminocarbonyl or arylaminocarbonyl substituted amide,carbazate or hydrazide derivatives.

Reacting AHP's with ketones and aldehydes such as acetone, 2-butanone,2-hexanone, cyclohexanone, 4-methylcyclohexanone,4-t-butylcyclohexanone, formaldehyde, acetaldehyde, benzaldehyde,p-methoxybenzaldehyde and furfuraldehyde, results in the formation ofSchiff base or hydrazone derivatives.

Reacting AHP's with alkylating agents, such as alkyl and aralkyl halides(bromides and chlorides) and sulfates, alkylsulfonates andarylsulfonates, and epoxides, such as ethylene oxide, propylene oxideand epichlorohydrin, results in the formation of N-alkyl substitutedamide, carbazate or hydrazide derivatives.

Reacting AHP's with organic or mineral acids, such as formic acid,acetic acid, chloroacetic acid, trifluoroacetic acid, lauric acid,adipic acid, benzoic acid, phthalic acid, trimellitic acid,methylsulfonic acid, p-methylphenylsulfonic acid, hydrochloric acid,hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid andperchloric acid, results in salt formation.

Non-limiting examples of the derivatives of the novel AHP's include thefollowing:

Derivatives of AHP's

1-Benzoyl-2-(4,4-di-[t-butylperoxy]pentanoyl)hydrazine

1-(2-Ethylhexoxycarbonyl]-2-[4,4-di-[t-butylperoxy]pentanoyl)hydrazine

3-Oxapentane-1,5-diyl bis(2-[4,4-di-(t-butylperoxy)pentanoyl]carbazate)

2,2,'-Di-(3,3-di-[t-butylperoxy]butanoyl) dodecanedioic acid dihydrazide

N'-(3-Carboxypropionyl)O-(1,3-dimethyl-3-[t-butylperoxy]butyl)carbazate, also known by thealternate name 1,3-Dimethyl-3-(t-butylperoxy)butyl3-(3-carboxypropionyl)carbazate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-phthalimido carbamate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl)N-([3,4,5,6-tetrabromo]phthalimido) carbamate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl)N-[(3,4,5,6-tetrachloro]phthalimido) carbamate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-([4-carboxy]phthalimido)carbamate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-([4-nitro]phthalimido)carbamate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-maleimido carbamate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-succinimido carbamate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-(2-decylsuccinimido) carbamate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-(2-[1-decenyl]succinimido)carbamate

O-(1,3-Dimethyl-3-[2-ethylhexanoylperoxy]butyl) N-maleimido carbamate

O-(1,3-Dimethyl-3-[2-ethylhexanoylperoxy]butyl) N-succinimido carbamate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-(2-succinimidoethyl) carbamate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-(2-phthalimidoethyl) carbamate

N-Succinimido 4,4-di-(t-butylperoxy)pentamide

N-Phthalimido 3,3-di-(t-butylperoxy)butanamide

N-(1-Methyl-1-[4-(1-methyl-1-[t-butylperoxy]ethyl)phenyl]ethyl)phthalimide

N-(1-Methyl-1-[4-(1-methyl-1-[t-butylperoxy]ethyl)phenyl]ethyl)succinimide

N-(1-Methyl-1-[4-(1-methyl-1-[t-butylperoxy]ethyl)phenyl]ethyl)maleimide

3-(1,4,4,6-Tetramethyl-2,3,7-trioxacycloheptyl)-N'-(3-carboxypropionyl)propionhydrazide

1-(1-Amino-1-methylethyl)-4-(1-methyl-1-[t-butylperoxy]ethyl)benzenehydrochloride salt

1-(1-Amino-1-methylethyl)-4-(1-methyl-1-[t-butylperoxy]ethyl)benzenep-toluenesulfonic acid salt

1,3-Dimethyl-3-(t-butylperoxy)butyl carbazate hydrochloride salt

Performance Additive Derivatives

Novel performance additive derivatives of the AHP's of the presentinvention for polymers can be synthesized by reacting the AHP's withperformance additive compounds that are co-reactive with the aminofunctional group of the AHP's. As used herein, the term "performanceadditive" relates to a compound or composition having functional groupsor moieties which enhance the performance of polymers or other compoundsor compositions to which they are added. For example, the performanceand use of polymers will be enhanced by ultraviolet ("UV") stabilizers,hindered amine light stabilizers ("HALS"), and flame retardants, amongothers. Bases useful in these reactions include the bases listed above.

Co-reactive performance additive compounds which may be reacted with theAHP's of the present invention include, for example,2-cyano-3,3-diphenylpropenoyl chloride,2-(4-benzoyl-3-hydroxyphenoxy)ethyl chloroformate,2-(4-benzoyl-3-hydroxyphenoxy)propyl chloroformate,(4-benzoyl-3-hydroxyphenoxy)acetyl chloride,2-(4-benzoyl-3-hydroxyphenoxy)propionyl chloride,2-(4-[2H-benzotriazol-2-yl]-3-hydroxyphenoxy)ethyl chlorocarbonate,2-(3-[2H-benzotriazol-2-yl]-4-hydroxyphenoxy)ethyl chlorocarbonate,4-(2H-benzotriazol-2-yl)-3-hydroxyphenoxyacetyl chloride,3-(2H-benzotriazol-2-yl)-4-hydroxyphenoxyacetyl chloride, dimethyl4-(2-chlorocarbonyl-oxyethoxy)benzylidenemalonate, diethyl4-(2-chlorocarbonyloxyethoxy)benzylidenemalonate, dipropyl4-(chlorocarbonylmethoxy)benzylidenemalonate,2,2,6,6-tetramethyl-4-piperidinyl chloroformate and2,2,6,6-tetramethyl-4-piperidone.

Non-limiting examples of the performance additive derivatives of thenovel AHP's include the following:

AHP-Performance Additive Derivatives

UV Stabilizer-Peroxides

1-(2-Cyano-3,3-diphenylpropenoyl)-2-(4,4-di-[t-amylperoxy]pentanoyl)hydrazine

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl)N'-(2-[4-benzoyl-3-hydroxyphenoxy]ethoxycarbonyl) carbazate

O-(2-[4-(2,2-Di[methoxycarbonyl]ethenyl)phenoxy]ethyl)N'-(4,4-di-[t-amylperoxy]pentanoyl) carbazate

HALS-Peroxides

2,2,6,6-Tetramethyl-4-piperidinyl-(4,4-di-[t-butylperoxy]pentanoyl)hydrazone

O-(2,2,6,6-Tetramethyl-4-piperidinyl)N'-(1,3-dimethyl-3-[t-butylperoxy]butyl) carbazate

O-(2,2,6,6-Tetramethyl-4-piperidinyl)N-(2-[1,3-dimethyl-3-(t-butylperoxy)butoxycarbonylamino]ethyl) carbamate

Coupled Peroxide Derivatives

Novel coupled peroxide derivatives of the AHP's of the present inventioncan be synthesized by reacting the AHP's with coupling agents that areco-reactive with the amino functional groups of the AHP's. Optionalbases useful in these reactions include the bases listed above. Reactionconditions are those which affect coupling of the AHP's and are wellknown to those skilled in the art or would be readily discernible basedon the disclosure herein.

The coupled peroxide derivatives within Structure A of the presentinvention reduce the volatility of the peroxides, rendering them lessfugitive in polymeric compositions. The coupled peroxides, which mayinclude polyperoxides, can be used to make higher molecular weightpolymers when used as free radical initiators.

Coupling agents which may be reacted with the AHP's of the presentinvention include, for example, sulfuryl chloride; phosgene; diacidchlorides, such as oxalyl chloride, succinoyl chloride, adipoylchloride, 1,12-dodecanedioyl chloride and terephthaloyl chloride;bischloroformates such as ethylene glycol bischloroformate, diethyleneglycol bischloroformate, neopentyl glycol bischloroformate and BisphenolA bischloroformate; diisocyanates such as hexamethylene diisocyanate,toluene diisocyanate, 4,4'-methylene bis(phenylisocyanate) andisophorone diisocyanate; and dianhydrides such as pyromelliticdianhydride, benzophenone dianhydride and ethylenebis(anhydrotrimellitate).

Non-limiting examples of the coupled peroxide derivatives of the novelAHP's include the following:

Coupled Peroxides

N,N'-Bis(2-[1,3-dimethyl-3-(t-butylperoxy)butoxycarbonylamino]ethyl)pyromellitic diimide

N,N'-Bis(4,4-di-[t-butylperoxy]pentamido) pyromellitic diimide

N,N'-Di-(1-methyl-1-[4-(1-methyl-1-[t-butylperoxy]ethyl)phenyl]ethyl)urea

N,N'-Bis(1-methyl-1-[4-(1-methyl-1-[t-butylperoxy]ethyl)phenyl]ethyl)pyromellitic diimide

N,N'-Di-(1-methyl-1-[4-(1-methyl-1-[t-butylperoxy]ethyl)phenyl]ethyl)succinamide

N,N,-Di-(1-methyl-1-[4-(1-methyl-1-[t-butylperoxy]ethyl)phenyl]ethyl)terephthalamide

Sequential Peroxide Derivatives

A sequential peroxide is defined as a compound with two or more peroxidegroups having different half-lives which decompose at differenttemperatures. They are particularly useful in making peroxy polymers,that is, polymers with peroxide end groups. Lower temperatures decomposethe shorter half-life peroxide to yield free radicals and initiatepolymerization. The peroxide group with the longer half-life forms blockcopolymers at higher temperatures. If a homopolymer is made from thesequential (di)peroxide, it can have higher molecular weight than if twoindividual peroxides having the half-life characteristics of thesequential (di)peroxide are used to make the homopolymer. The sequential(di)peroxide is also advantageously less volatile than two individualperoxides having the half-life characteristics of the sequential(di)peroxide.

Novel sequential peroxide derivatives of the AHP's of the presentinvention can be synthesized by reacting the AHP's of this inventionwith peroxy compounds having decomposition kinetics different than thoseof the AHP's and which are co-reactive with the amino functional groupsof the AHP's. Optional bases useful in these reactions include the baseslisted above. Reaction conditions are those which affect reaction of theAHP's and the co-reactive peroxy compounds and are well known to thoseskilled in the art or would be readily discernible based on thediclosure herein.

Co-reactive peroxy compounds which may react with the AHP's of thepresent invention include, for example, 2-(t-butylperoxycarbonyl)benzoylchloride, 3-(t-butylperoxycarbonyl)propionyl chloride,4-(t-amylperoxycarbonyl)butyryl chloride, 4,4-di-(t-butylperoxy)pentylchloroformate, 1,3-dimethyl-3-(t-butylperoxy)butyl chloroformate,3-methyl-3-(t-butylperoxy)butyl chloroformate,1,3-dimethyl-3-(t-amylperoxy)butyl chloroformate,1,3-dimethyl-3-(2-ethyl-hexanoylperoxy)butyl chloroformate,1,3-dimethyl-3-(neoheptanoylperoxy)butyl chloroformate,di-(1,1-dimethyl-3-chlorocarbonyloxybutyl) peroxide,di-(1,1-dimethyl-3-chlorocarbonyloxypropyl) peroxide and4,4-di-(t-butylperoxy)pentanoic acid anhydride.

Non-limiting examples of sequential peroxide derivatives of the novelAHP's include the following:

Sequential Peroxides

O-(1,3-Dimethyl-3-[t-butylperoxy])butyl)N'-(3-[t-butylperoxycarbonyl]propionyl) carbazate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl)N'-(2-[t-butylperoxycarbonyl]benzoyl) carbazate

O-(1,3-Dimethyl-3-[2-ethylhexanoylperoxy]butyl)N'-(1,3-dimethyl-3-[t-butylperoxy]butoxycarbonyl) carbazate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl)N'-(3,3-di-[t-butylperoxy]butanoyl) carbazate

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl)N'-(4,4-di-[t-amylperoxy]pentanoyl) carbazate

Polymeric Peroxide Derivatives

Novel polymeric peroxide derivatives of the AHP's of the presentinvention can be synthesized by reacting the AHP's of this inventionwith anhydride polymers or copolymers, lower alkyl hydrogen maleatepolymers or copolymers, lower alkyl hydrogen fumarate polymers orcopolymers, and lower alkyl acrylate and methacrylate copolymers inwhich at least one of the co-momomers is acrylic acid, methacrylic acid,maleic acid or fumaric acid.

In general, any addition polymer or copolymer of ethylenic monomers andcontaining cyclic anhydride groups, either on the polymer backbone orgrafted side chains, is suitable for attachment of the AHP's to form theperoxy polymer derivatives of the AHP's of this invention. Due to costand ease of preparation, the anhydride containing polymers arepreferably polymers or copolymers of maleic anhydride, although polymersor copolymers of other cyclic anhydrides may be used to form thepolymeric peroxide derivatives of the AHP's of the present invention.

Suitable anhydride containing copolymers useful for employment in thisinvention include but are not limited to: (a) styrene-maleic anhydridecopolymers; (b) alternating copolymers of maleic anhydride andalpha-olefins; (c) copolymers of alkyl vinyl ethers and maleicanhydride; (d) maleic anhydride modified polyolefins; (e) maleicanhydride adducts of hydrogenated polymers or copolymers; (f) maleicanhydride adducts of EPDM; and (g) other anhydride copolymers.

The styrene/maleic anhydride copolymers employed in this invention are ageneral class of compounds consisting of the alternating copolymers ofstyrene and maleic anhydride, or the non-equimolar copolymers containingless than about 50 mole percent of the anhydride monomer. The styrenemay be replaced in whole or in part by other vinylaromatic monomers suchas alpha-methylstyrene, nuclear methylstyrenes, ethylstyrene,isopropylstyrene, t-butylstyrene, chlorostyrenes, dichlorostyrenes,bromostyrenes, dibromostyrenes, vinylnaphthalene and the like.Similarly, the maleic anhydride can be replaced in whole or in part byanother alpha, beta-unsaturated cyclic dicarboxylic acid anhydride suchas itaconic, aconitic, citraconic, mesaconic, chloromaleic, bromomaleic,dichloromaleic, dibromomaleic, phenylmaleic and the like. The preferredalpha, beta-unsaturated cyclic anhydride is maleic anhydride. Thecopolymer may also contain a termonomer, such as a C₁ to C₃ alkylacrylate or methacrylate, acrylonitrile, methacrylonitrile, acrylamide,methacrylamide, acrylic acid or methacrylic acid.

Suitable copolymers may be prepared by any of the several methodsavailable for the preparation of styrene-maleic anhydride copolymers orthey may be purchased commercially. Non-equimolar copolymers may beprepared by solution polymerization directly from the respectivemonomers by the incremental addition of the reactive monomer as taughtby U.S. Pat. No. 2,971,939; by a continuous recycle polymerizationprocess, such as described in U.S. Pat. Nos. 2,769,804 and 2,989,517; bythe suspension polymerization process described in U.S. Pat. No.3,509,110 or by numerous known variations. The disclosure of each ofthese patents is hereby incorporated herein by reference.

Also suitable are the rubber-modified copolymers where 5 to 40 -percentby weight of one of the known elastomers has been incorporated into thevinylaromatic-alpha, beta-unsaturated dicarboxylic acid anhydridecopolymer. The elastomers may be incorporated into the anhydridecopolymers by blending, mixing or copolymerizing the monomers in thepresence of the rubber.

Suitable rubbers or elastomers include conjugated 1,3-diene rubbers,styrene/diene copolymer rubbers, acrylonitrile/diene copolymer rubbers,ethylene/propylene copolymer rubbers, ethylene/propylene/dieneterpolymer rubbers, acrylate/diene copolymer rubbers, and mixturesthereof.

Preferred rubbers are diene rubbers such as homopolymers of conjugateddienes such as butadiene, isoprene, chloroprene, and piperylene andcopolymers of such dienes with up to 50 mole percent of one or morecopolymerizable mono-ethylenically unsaturated monomers, such asstyrene, substituted styrenes, acrylonitrile, methacrylonitrile andisobutylene.

Preferably, the elastomers are incorporated into the monomer mixtureprior to polymerization using, for example, the method of U.S. Pat. Nos.4,097,551 or 4,486,570 in which a mixture of at least two rubberyadditives is present during the polymerization. The disclosures of thesepatents are hereby incorporated herein by reference.

Particularly suitable for use are the non-equimolar copolymers ofstyrene and maleic anhydride designated Dylark™ copolymers, commerciallyavailable from ARCO Chemical Company division of Atlantic RichfieldCompany. Suitable Dylark™ copolymers include those of the 200 series andthe 300 series and Dylark™ 700 copolymer. Those copolymers designatedDylark™ 250, Dylark™ 350 and Dylark™ 700 are impact modified.

The SMA™ resins available from ARCO Chemical Company are low molecularweight styrene/maleic anhydride copolymers (MW 700-1900), for example.SMA™ 1000, 2000 and 3000 are also useful in this invention.

Also suitable are the styrene/maleic anhydride copolymers or rubbermodified styrene/maleic anhydride copolymers where a portion of themaleic anhydride groups are converted to maleimide groups orN-substituted maleimide groups. The partially imidated copolymers can beprepared by treating the styrene/maleic anhydride copolymer with aprimary amine in a post polymerization step as described in U.S. Pat.No. 3,998,907 or during the polymerization as described in U.S. Pat. No.4,381,373, the disclosures of which are hereby incorporated byreference. The molar ratio of the amine to the maleic anhydride in thecopolymer should be less than 0.8 to allow attachment of the peroxidegroups via the amino or hydrazino groups of the AHP's. The formation ofthe maleimide groups that do not contain peroxide groups may be formedbefore, during or after the formation of the maleamic acid or maleimidegroups containing peroxide groups. Suitable amines for this purpose areammonia, primary alkyl amines and primary aryl amines.

The styrene/maleic anhydride copolymer may optionally contain atermonomer such as a C₁ to C₃ alkyl acrylate or methacrylate,acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, acrylicacid or methacrylic acid. Rubber modified terpolymers of styrene, maleicanhydride and lower alkyl (C₁ to C₃) methacrylates are described in U.S.Pat. No. 4,341,695. The polymeric composition is conveniently preparedby dissolving the rubber in a solution of the monoalkenyl aromaticcomponent and the methacrylate ester in a suitable solvent and thenpolymerizing the solution with the anhydride component in the mannerdescribed in, for example, U.S. Pat. Nos. 2,971,939, 3,336,267 and3,919,354. The disclosures of the latter two patents are herebyincorporated herein by reference.

The Cadon™ resins (Monsanto Chemical Company) are a commercial series ofstyrene/maleic anhydride polymer alloys withacrylonitrile/butadiene/styrene (ABS). Rubber-modified versions are alsoavailable. These resins are also suitable for this invention.

Also suitable are the rubber modified styrene maleic anhydride resinsdescribed in U.S. Pat. No. 4,522,983 where a minor amount of a nuclearsubstituted methylstyrene is included in the composition. The disclosureof this patent is hereby incorporated herein by reference.

The styrene/maleic anhydride polymers may be further modified bycopolymerizing the monomers in the presence of other monomers. Inaddition to the acrylates, methacrylates, acrylonitrile andmethacrylonitrile previously mentioned, other suitable monomers includethe ethylenically unsaturated carboxylic acids, preferably acrylic andmethacrylic acids, acrylamide and methacrylamide, dialkylamino C₁ to C₆alkyl acrylates or methacrylates, such as dimethylaminoethyl acrylate ormethacrylate, and vinyl esters derived from saturated carboxylic acidsof 2 to 22 carbon atoms, such as vinyl acetate or vinyl propionate.

Further modification of the styrene/maleic anhydride copolymers can beaccomplished by carrying out the copolymerization in the presence ofcrosslinking monomers having two or more ethylenically unsaturateddouble bonds such as divinylbenzene, 1,4-butadiene, divinyl ether,ethylene glycol dimethacrylate, butanediol dimethacrylate, triallylcyanurate and similar type compounds. The crosslinking monomers areemployed in amounts of from 0.01 to 5, preferably from 0.1 to 2 molepercent based on maleic anhydride.

Alternating copolymers of maleic anhydride and alpha-olefins are wellknown in the art, as exemplified by U.S. Pat. Nos. 3,553,177, 3,560,455,3,560,456 and 3,560,457. Each of these patents describes a copolymer ofmaleic anhydride with a specific alpha-olefin such as C₁₂ to C₃₀alpha-olefins. The copolymers of C₆ to C₁₀ alpha-olefins are known asdisclosed by U.S. Pat. No. 3,488,311. Terpolymers of maleic anhydrideand at least one lower alpha-olefin and at least one higher alpha-olefinare also known, as disclosed by U.S. Pat. No. 4,358,573. The disclosuresof the patents referred to in this paragraph are hereby incorporatedherein by reference.

The alternating copolymers may be prepared by conventionalpolymerization processes including those described in U.S. Pat. Nos.3,553,177, 3,560,455, 3,560,456, 3,560,457 and 3,488,311, thedisclosures of which are hereby incorporated herein by reference. PA-18™(Chevron Chemical Company) is an example of a commercially availablealternating copolymer of maleic anhydride and octadecene-1.

Also suitable for this invention are the terpolymers disclosed in U.S.Pat. Nos. 4,522,992 and 3,723,375, the disclosures of which are herebyincorporated herein by reference. These are basically terpolymers ofcyclic alpha, betaunsaturated dicarboxylic acid anhydrides, aromaticmono-alkenyl monomers and higher 1-alkenes. Preferably, they areterpolymers of styrene, maleic anhydride and alpha-olefins having 10 ormore carbon atoms. Both pure alkenes and mixed alkenes can be utilizedin preparing the terpolymers.

Alternating copolymers of alkyl vinyl ethers and maleic anhydride arereadily prepared in bulk or solution using free radical initiators (e.g.lauroyl peroxide) as disclosed in British Patent 1,117,515, thedisclosure of which is hereby incorporated herein by reference. Low,medium and high molecular weight grades are commercially available.Commercial grades include the Gantrez™ resins (GAF Corp.). Suitablealkyl vinyl ethers for this invention include methyl, ethyl, propyl,isopropyl, n-butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl,2-ethylhexyl, nonyl, decyl, dodecyl, hexadecyl and octadecyl vinylethers.

The maleic anhydride modified polyolefins employed in this inventionhave the general formula: ##STR17## where R_(i) and R_(ii) are aspreviously defined and P'-represents an olefin polymer residue which isbased on a preponderance of ethylene, propylene or 1-butene, and havinga valence of p. It can be either a high or low density polyethyleneresidue, a polypropylene residue or a residue of a copolymer of ethylenewith 1-butene, a residue of a copolymer of ethylene and propylene, aresidue of a propylene-butene copolymer or a residue of such a propylenecopolymer with an olefin having up to about six carbon atoms.

The maleic anhydride-modified polyolefins are known materials containingabout 0.2 to 9% by weight of combined maleic anhydride, preferably about2 to 5%. In fact, one embodiment of these materials is a commerciallyavailable product, Hercoprime™ by Hercules Incorporated. Polyethylene orpolypropylene modified with maleic anhydride is available commerciallyas Plexar™ from Enron Chemical Co. Any polymer or copolymer of ethylene,propylene, or 1-butene can be modified via the maleic anhydride moietyto form the substrate molecule, including polyethylene, polypropylene,ethylene/propylene copolymer, propylene/butene-1 copolymer, orbutene-1/-ethylene copolymer. The most frequently encountered and thepreferred maleic anhydride modified polyolefin is that based onpolypropylene.

The preparation of maleic anhydride modified polypropylene is describedin, inter alia, U.S. Pat. No. 3,483,276, the disclosure of which ishereby incorporated herein by reference. Briefly, the preparationconsists of treating the olefin polymer with a material or by meanswhich will induce the formation of active, free radical sites thereofwith which maleic anhydride can react. Active centers can be induced,e.g. by subjecting the polymer to the action of high energy ionizingradiation such as gamma rays, X-rays, or high speed electrons; bycontacting it, either as a solid or a solution in a solvent, with a freeradical initiator, such as dibenzoyl peroxide, dilauroyl peroxide,dicumyl peroxide or t-butyl peroxybenzoate; or by simply milling it inthe presence of air. The preferred method is the reaction of thepolyolefin with maleic anhydride in solvent solution in the presence ofa free radical initiator.

The olefin polymer based maleamic acids and maleimides of the inventionare prepared by graft modifying the appropriate polymer backbone with amaleic anhydride and thereafter reacting the anhydride modified olefinpolymer with the AHP's containing primary amino or hydrazidefunctionalities. A less preferred method is to modify the appropriatepolymer backbone with N(peroxide substituted)-maleimides of formula:##STR18## where R_(i), R_(ii) and are as previously defined.

The graft modification of EPDM by maleic anhydride in the presence ofdicumyl peroxide and benzoyl peroxide is described by DeVito andco-workers (G. DeVito, N. Lanzetta, G. Maglio, M. Malinconico, P. Musta,R. Palumbo, J. Polym. Sci., Polym. Chem., Ed., 22, pp-1335-47 (1984)),the disclosure of which is hereby incorporated herein by reference.

U.S. Pat. No. 4,506,056, the disclosure of which is hereby incorporatedherein by reference, describes a process for grafting maleic anhydrideonto molten polymers or copolymers using a free radical catalyst inwhich crosslinking or degradation of the polymers is controlled oreliminated in the presence of scavengers which inhibit thehomopolymerization of maleic anhydride.

The maleic anhydride adduct polymers useful in this invention arepolymeric products containing pendant succinic anhydride groups whichare formed by reacting maleic anhydride with hydrogenated polymers ofconjugated dienes or hydrogenated copolymers of conjugated dienes andvinyl aromatic hydrocarbons containing a residual unsaturation level offrom 0.5 to 20 percent of their original unsaturation level prior tohydrogenation. The reaction which is conducted by heating a mixture ofthe maleic anhydride and hydrogenated polymer or copolymer containingresidual unsaturation proceeds by means of a reaction mechanism referredto as an "ene" reaction well known to those skilled in the art. Themaleic anhydride adds to the unsaturation of the polymer to form thepolymer product containing the pendant succinic anhydride groups. Byvirtue of the pendant anhydride groups, this polymer can be reacted withperoxides containing primary amino or hydrazide groups to form thepolymer bound peroxides of this invention.

The amounts of maleic anhydride employed in the reaction can varyconsiderably depending on the specific nature of the hydrogenatedpolymer and the properties desired in the final product. In general, theamount of maleic anhydride employed may range from 0.1 to about 25percent by weight based on the total weight of maleic anhydride andhydrogenated polymer with a preferred amount being from 0.2 to 5 percentby weight.

Various polymers of conjugated dienes and copolymers of conjugateddienes and vinyl aromatic hydrocarbons may be hydrogenated for use inpreparing the maleic anhydride adduct component of the compositions ofthe invention. Polymers of conjugated dienes which may be hydrogenatedinclude polymers derived from one or more conjugated diene monomers.Thus, polymers derived from a single conjugated diene such as, forexample, 1,3-butadiene (i.e. a homopolymer) or polymers derived from twoor more conjugated dienes such as, for example, 1,3-butadiene andisoprene or 1,3-butadiene and 1,3-pentadiene (i.e. a copolymer), and thelike, may be utilized. Copolymers which may be hydrogenated includerandom copolymers of conjugated dienes and vinyl aromatic hydrocarbonsand block copolymers of conjugated dienes and vinyl aromatichydrocarbons which exhibit elastomeric properties.

Examples of polymers of conjugated dienes and random and blockcopolymers of conjugated dienes and vinyl aromatic hydrocarbons that canbe utilized in the invention are described in European PatentPublication No. 103,148, published Mar. 21, 1984, based on EuropeanPatent Application No. 83107732.6, filed May 8, 1983. Many of thesepolymers and copolymers are commercially available and they may behydrogenated by a variety of well established processes. Suitablehydrogenation processes are described in U.S. Pat. Nos. 3,113,986 and4,226,952. The disclosures of the European Patent Application and theU.S. Patents referred to in this paragraph are hereby incorporatedherein by reference.

The maleic anhydride adduct is prepared by a relatively uncomplicatedprocess which does not require complex copolymerization or graftingprocedures. It can be prepared by first forming a homogeneous mixture orsolution of the maleic anhydride and the hydrogenated polymer orcopolymer containing residual unsaturation and then reacting theresultant mixture or solution under appropriate conditions of time andtemperature. Examples of appropriate reaction conditions are given inEuropean Patent Publication No. 103,148.

The maleic anhydride adducts of EPDM are also suitable maleic anhydridepolymers for attachment of reactive peroxide groups. They are preparedby the thermal addition of maleic anhydride to elastomeric copolymers ofethylene and propylene which have a substantially saturated hydrocarbonbackbone chain and unsaturated hydrocarbon side-chains. The preparationof these adducts is described in U.S. Pat. No. 3,884,882, the disclosureof which is hereby incorporated herein by reference.

Examples of other anhydride copolymers that are suitable for use in thisinvention for attaching peroxide groups to polymer backbones via amicacid or imide formation include the following non-limiting list:

1) vinyl acetate/maleic anhydride copolymer;

2) ethylene/vinyl acetate/maleic anhydride terpolymer;

3) isobutylene/maleic anhydride copolymer;

4) graft polyols containing styrene/maleic anhydride copolymer in thegrafted chain;

5) Styrene/maleic anhydride-2,4,6-tribromophenyl acrylate terpolymer;

6) maleic anhydride/divinylbenzene/styrene terpolymer;

7) ethylene/maleic anhydride/styrene graft copolymer;

8) methyl methacrylate/maleic anhydride copolymers;

9) butyl methacrylate/maleic anhydride/styrene terpolymer; and

10) ethylene/maleic anhydride copolymers (available from MonsantoChemical Company).

Other suitable maleic anhydride copolymers include the terpolymers ofanhydrides, aromatic mono-alkenyl monomers and higher 1-alkenesdescribed in U.S. Pat. No. 4,522,992, the tribromophenylacrylate/epichlorohydrin/maleic anhydride/styrene copolymer described inU.S. Pat. No. 4,108,943, and the methyl methacrylate/maleicanhydride/styrene copolymers disclosed in Japanese Patent Publications59,221,314 and 59,221,315, both dated Dec. 12, 1984, relating toJapanese Patent Applications 83/95,070 and 83/95,071, respectively, bothfiled May 31, 1983, abstracted in Chem. Abst. (102: 150317x and150318y), divinyl ether/maleic anhydride copolymers from Adica Labs(Pivan), a polybutadiene/polystyrene/maleic anhydride terpolymerreferred to as Ricoh™ 184/MA, a product of Colorado ChemicalSpecialties, Inc., and ethylene/vinyl acetate copolymer grafted withmaleic anhydride such as Modic E 310 K a product of Mitsubishi ChemicalIndustries Co.

Poly(maleic anhydride) such as Belcene, a product of Ciba-Geigy Corp.,is also suitable in this invention.

Anhydride polymers containing glutaric anhydride units (i.e., wheret=1), as opposed to those containing succinic anhydride units (i.e.,where t=0), can also be used in the practice of this invention. Suchpolymeric anhydrides (i.e., those with glutaric anhydride units) areavailable from polymers and copolymers of acrylic acid and methacrylicacid by heating under dehydrating conditions, with or without a catalyst(European Patent Publication No. 76,691, published Apr. 13, 1983, basedon European Patent Application 82350285.7, filed Oct. 5, 1982), or fromhomopolymerizing or copolymerizing acrylic acid anhydride or methacrylicacid anhydride under a variety of conditions.

The polymeric amic acid derivatives of the AHP's that are derived fromcyclic anhydride-containing polymers and copolymers can be prepared byreacting the AHP's and the cyclic anhydride-containing polymers andcopolymers in solution, at temperatures in the range of about 0° C. toabout 180° C., followed by isolation of the polymeric amic acidperoxides. The polymeric imide derivatives of the AHP's can be preparedfrom the above polymeric amic acid peroxides or mixtures of the AHP'sand anhydride-containing polymers and copolymers by azeotroping waterfrom solution or by reacting with effective amounts of, preferably,acetic anhydride and sodium acetate in solution, at temperatures in therange of about 40° C. to about 180° C., followed by isolation of thepolymeric imide peroxides (British Patent 1,307,409, Example 3). Anon-limiting list of solvents useful in these reactions include aromaticsolvents, such as benzene, toluene, xylenes, mesitylene, ethyl benzene,cumene and others, and dimethyl sulfoxide, dimethylformamide,gamma-butyrolactone and propylene carbonate.

Alternately, the polymeric amic acid derivatives of the AHP's can beprepared by reacting the anhydride containing polymers with AHP's inpolymer mixing equipment such as extruders, etc., at temperaturesbeginning in the range of the softening point of the anhydridecontaining polymer, about 80° C., to about 180° C., no solvent beingused. The polymeric imide derivatives of the AHP's are more difficult toprepare in polymer mixing equipment owing to significant thermaldecomposition of the peroxide groups at the temperatures required todehydrate and cyclize the amic acid group to the imide group, i.e., 180°C. to 300° C. It is unimportant to form imide linkage in polymer mixingequipment, since the amic acid linkage of the peroxide group to thepolymer is just as effective as the imide linkage in applications ofpolymeric peroxides. Once the peroxide group of the polymeric amic acidperoxide has been used (decomposed) in an application, the amic acidlinkages of the non-peroxidic polymeric product can be converted at thehigher temperatures to the more thermally stable imide linkages.However, owing to lower solution viscosities of peroxy polymers withimide linkages compared to those with amic acid linkages, the polymericimide derivatives of the AHP's are preferred, from the handling point ofview.

Suitable lower alkyl hydrogen maleate copolymers useful for preparationof the novel polymeric peroxide derivatives from the non-polymeric AHP'sof Structure A include copolymers such as ethylene/alkyl acrylate/alkylhydrogen maleate or ethylene/alkyl methacrylate/alkyl hydrogen maleateterpolymers.

Other novel polymeric peroxide derivatives of the AHP's of thisinvention can be synthesized by reacting the AHP's of this inventionwith polymers possessing pendant acid groups (formation of polymers withpendant ammonium-peroxide or hydrazinium-peroxide salts or pendantamide-peroxide or hydrazide-peroxide groups), polymers possessingpendant isocyanate groups (formation of polymers with pendanturea-peroxides or pendant semi-carbazide-peroxide groups), polymerspossessing pendant epoxy groups (formation of polymers with pendanthydroxyalkylamino- or hydroxyalkyl-hydrazino-peroxide groups), polymerswith pendant halide (bromide or chloride) groups (formation of polymerswith pendant amino-peroxide or hydrazino-peroxide groups), polymerspossessing pendant aldehyde or ketone functions (formation of polymerswith pendant Schiff base- (imino-) peroxide or hydrazone-peroxidegroups), polymers possessing pendant ester or carboxylic acid chloridegroups (formation of polymers with pendant amide-peroxide orhydrazide-peroxide groups), polymers possessing pendant chloroformategroups (formation of polymers with pendant carbamate-peroxide orcarbazate-peroxide groups) or polymers possessing pendant oxazolinegroups (formation of polymers with pendant amidoethyleneamino-peroxideor amidoethylenehydrazino-peroxide groups).

Still other novel polymeric peroxide derivatives of the AHP's of thisinvention can be synthesized by reacting the AHP's of this inventionwith polymers possessing the above named pendant groups as end-groupsinstead of pendant groups. Polymers with corresponding peroxideend-groups are formed.

Utility of The AHP's Polymerization of Ethylenically UnsaturatedMonomers

The novel AHP's of Structure A of this invention were found to beeffective initiators with respect to efficiency (reduced initiatorrequirements, etc.) in the free-radical polymerizations of ethylenicallyunsaturated monomers at suitable temperatures and pressures.Ethylenically unsaturated monomers include olefins, such as ethylene,propylene, styrene, alpha-methylstyrene, p-methylstyrene,chlorostyrenes, bromostyrenes, vinylbenzyl chloride, vinylpyridine anddivinylbenzene; diolefins, such as 1,3-butadiene, isoprene andchloroprene; vinyl esters, such as vinyl acetate, vinyl propionate,vinyl laurate, vinyl benzoate and divinyl carbonate; unsaturatednitriles, such as acrylonitrile and methacrylonitrile; acrylic acid andmethacrylic acid and their anhydrides, esters and amides, such asacrylic acid anhydride, methyl, ethyl, t-butyl, 2-hydroxyethyl, lauryland 2-ethylhexyl acrylates and methacrylates, and acrylamide andmethacrylamide; maleic anhydride and itaconic anhydride; maleic,itaconic and fumaric acids and their esters; vinyl halo and vinylidenedihalo compounds, such as vinyl chloride, vinyl bromide, vinyl fluoride,vinylidene chloride and vinylidene fluoride; perhalo olefins, such astetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene;vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether and t-butylvinyl ether; allyl esters, such as allyl acetate, allyl benzoate, allylethyl carbonate, triallyl phosphate, diallyl phthalate, diallylfumarate, diallyl glutarate, diallyl adipate, diallyl carbonatediethylene glycol bis(allyl carbonate) (i.e., ADC); acrolein; methylvinyl ketone; and mixtures thereof.

Temperatures of about 0° C. to about 250° C., preferably about 30° C. toabout 200° C., and AHP levels (on a pure basis) of about 0.002 to about3%, preferably about 0.002 to about 1% by weight based on monomer, arenormally employed in conventional polymerizations and copolymerizationsof ethylenically unsaturated monomers.

The AHP's of this invention can be used in combination with otherfree-radical initiators including, for example, peroxyesters, such ast-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, t-butylperoxyacetate, t-amyl peroxypivalate, t-butyl peroxyneodecanoate, t-amylperoxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate andalpha-cumyl peroxyneodecanoate; dialkyl peroxydicarbonates, such asdi-n-propyl, diisopropyl, di-(sec-butyl), dicyclohexyl,di-(4-t-butylcyclohexyl), di-(2-phenoxyethyl), di-(2-ethylhexyl) anddihexadecyl peroxydicarbonates; acyl alkylsulfonyl peroxides, such asacetyl cyclohexylsulfonyl peroxide and acetyl sec-heptylsulfonylperoxide; diacyl peroxides, such as dibenzoyl peroxide, didodecylperoxide, diisobutyryl peroxide and di-(2-methylpentanoyl)peroxide;diperoxyketals such as, 2,2-di-(t-butylperoxy)butane,2,2-di-(t-butylperoxy)heptane, ethyl 3,3-di-(t-butylperoxy)butyrate,1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-di-(t-butylperoxy)cyclohexane and 1,1-di(t-amylperoxy)cyclohexane;monoperoxycarbonates such as OO-t-butyl O-isopropyl monoperoxycarbonateand OO-t-butyl O-(2-ethylhexyl) monoperoxycarbonate; dialkyl peroxides,such as 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane; and azo compounds,such as azo-bis(isobutyronitrile),2-t-butylazo-2-cyano-4-methoxy-4-methylpentane and1-t-butylazo-1-cyanocyclohexane. Using the AHP's in combination withthese initiators adds flexibility to the processes of polymer producersand allows them to "fine tune" their polymerization processes. Mixturesof two or more AHP's can also be used where appropriate.

Curing of Unsaturated Polyester Resins

In the curing of unsaturated polyester resin compositions by heating atsuitable curing temperatures in the presence of free-radical curingagents, the AHP's of Structure A of this invention exhibit enhancedcuring activity in the curable unsaturated polyester resin compositions.Unsaturated polyester resins that can be cured by the AHP's of thisinvention usually include an unsaturated polyester and one or moreethylenically unsaturated monomers.

The unsaturated polyesters are, for instance, polyesters as they areobtained by esterifying at least one ethylenically unsaturated di- orpolycarboxylic acid, anhydride or acid halide, such as maleic acid,fumaric acid, glutaconic acid, itaconic acid, mesaconic acid, citraconicacid, allylmalonic acid, tetrahydrophthalic acid, and others, withsaturated and unsaturated di- or polyols, such as ethylene glycol,diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediols, 1,2-,1,3- and 1,4-butanediols, 2,2-dimethyl-1,3-propanediols,2-hydroxymethyl-2-methyl-1,3-propanediol, 2-buten-1,4-diol,2-butyn-1,4-diol, 2,4,4-trimethyl-1,3-pentanediol, glycerol,pentaerythritol, mannitol and others. Mixtures of such di- or polyacidsand/or mixtures of such di- or polyols may also be used. The di- orpolycarboxylic acids may be partially replaced by saturated di- orpolycarboxylic acids, such as adipic acid, succinic acid, sebacic acidand other, and/or by aromatic di- or polycarboxylic acids, such asphthalic acid, trimellitic acid, pyromellitic acid, isophthalic acid andterephthalic acid. The acids used may be substituted by groups such ashalogen. Examples of such suitable halogenated acids are, for instance,tetrachlorophthalic acid, tetrabromophthalic acid,5,6-dicarboxy-1,2,3,4,7,7-hexachlorobicyclo-(2.2.1)-2-heptene andothers.

The other component of the unsaturated polyester resin composition, thepolymerizable monomer or monomers, can preferably be ethylenicallyunsaturated monomers, such as styrene, alpha-methylstyrene,p-methylstyrene, chlorostyrenes, bromostyrenes, vinylbenzyl chloride,divinylbenzene, diallyl maleate, dibutyl fumarate, triallyl phosphate,triallyl cyanurate, diallyl phthalate, diallyl fumarate, methylacrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate,ethyl acrylate, and other, or mixtures thereof, which arecopolymerizable with the unsaturated polyesters.

A preferred unsaturated polyester resin composition contains as theunsaturated polyester component the esterification product of1,2-propanediol (a polyol), maleic anhydride (an anhydride of anunsaturated polycarboxylic acid) and phthalic anhydride (an anhydride ofan aromatic dicarboxylic acid), as well as the monomer component,styrene.

Other types of unsaturated polyester resin compositions can be curedusing the AHP's of this invention as curing catalysts. These resins,called unsaturated vinyl ester resins, include a vinyl ester resincomponent and one or more polymerizable monomer components. The vinylester resin component can be made by reacting a chloroepoxide, such asepichlorohydrin, with appropriate amounts of a bisphenol such asBisphenol A (2,2-[4-hydroxyphenyl]propane), in the presence of a base,such as sodium hydroxide, to yield a condensation product havingterminal epoxy groups derived from the chloroepoxide. Subsequentreaction of the condensation product with polymerizable unsaturatedcarboxylic acids, such as acrylic acid and methacrylic acid, in thepresence or absence of acidic or basic catalysts well known to thoseskilled in the art, results in formation of the vinyl ester resincomponent. Normally, styrene is added as the polymerizable monomercomponent to complete the preparation of the unsaturated vinyl esterresin composition.

Temperatures of about 20° C. to about 200° C. and AHP levels of about0.05% to about 5% or more by weight of curable unsaturated polyesterresin composition are normally employed.

The unsaturated polyester resin compositions described above can befilled with various materials, such as sulfur, glass, carbon and boronfibers, carbon blacks, silicas, metal silicates, clays, metalcarbonates, antioxidants (AO's), heat, ultraviolet (UV) and lightstabilizers, sensitizers, dyes, pigments, accelerators, metal oxides,such as zinc oxide, blowing agents, nucleating agents and others.

Curing of Elastomers and Crosslinking of Thermoplastic Polymers

In the curing of elastomeric compositions, and the crosslinking ofpolymer compositions, by heating at suitable curing and crosslinkingtemperatures in the presence of free-radical curing and crosslinkingagents, the AHP's of Structure A of this invention exhibit curing andcrosslinking activities.

Elastomeric resin compositions that can be cured by the AHP's of thisinvention include elastomers such as ethylene/propylene copolymers(EPR), ethylene/propylene/diene terpolymers (EPDM), polybutadiene (PBD),silicone rubber (SR), nitrile rubber (NR), neoprene, fluoroelastomersand ethylene/vinyl acetate copolymer (EVA).

Polymer compositions that can be crosslinked by the AHP's of thisinvention include olefin thermoplastics such as chlorinated polyethylene(CPE), low density polyethylene (LDPE), linear-low density polyethylene(LLDPE), and high density polyethylene (HDPE). Other crosslinkablethermoplastic polymers include PVC, polystyrene, poly(vinyl acetate),polyacrylics, polyesters, polycarbonate, etc.

Temperatures of about 80° C. to about 310° C. and AHP levels of about0.1% to about 10%, preferably about 0.5% to about 5%, based on weight ofcurable elastomeric resin composition or crosslinkable olefin polymercomposition, are normally employed.

The curable elastomeric resin composition or crosslinkable polymercomposition optionally can be filled with the materials listed above foruse with the conventional unsaturated polyester resin compositions.

Modification of Polyolefins and Other Polymers

The AHP's of Structure A of this invention exhibit polyolefinmodification activity in processes for modifying polypropylene (PP) andcopolymers containing more than 50% by weight of PP. Modification of thePP polymers and copolymers includes, for example, beneficial degradationof PP by reducing the polymer molecular weight and modifying the polymermolecular weight distribution.

Temperatures of about 140° C. to about 340° C. and AHP levels of about0.01% to about 1.0% based on weight of modifiable PP polymers orcopolymers are normally employed. Optionally, up to about 1% by weightof molecular oxygen can be employed as a modification co-catalyst.

Utility of Polymeric Peroxide Derivatives

The novel polymeric peroxide derivatives of the AHP's of Structure Ahave utility in several applications. They can be used to prepare blockand graft copolymers by several techniques. A graft copolymer of thepolymeric peroxide derivative can be made by using the polymericperoxide derivative as the backbone polymer and as the initiator, andgrafting monomers onto this backbone. A graft copolymer of two or moremonomers that are not the same as the monomers of the polymeric peroxideof Structure A can be made by partially decomposing the polymericperoxide first in the presence of one monomer, followed by decompositionin the presence of a second monomer, etc. The latter processes can becarried out in solution or in polymer processing equipment such asextruders. Such graft copolymers have utility in compatibilizinghomopolymer and copolymer blends and alloys.

The polymeric peroxides of Structure A can also be used in reactiveprocessing to compatibilize polymers in situ by forming block and graftcopolymers in polymer processing equipment such as extruders, rollmills, etc. In the latter processes, the preformed polymeric peroxide orthe polymeric peroxide formed in situ from the anhydride and one or moreof the amino-containing compounds of Structure A may be used. If morethan one amino containing peroxide of Structure A is reacted with ananhydride-containing polymer, the resulting polymeric peroxide can haveperoxy functional groups on the backbone with a variety of activitiesand expanded utilities.

The polymeric peroxides can also be used to enhance the quality ofinterpenetrating polymer networks (IPN's) in polymer processingequipment.

Polymeric peroxides of Structure A derived from anhydride containingelastomeric polymers can be used in reactive processing to enhance theimpact resistance of polymer blends.

The polymeric peroxides of Structure A also have utility as polymericlow profile/low shrink curing agents, as self-curing polymeric systemsand as self degrading polymer systems.

Additionally, the polymeric peroxides of Structure A are very beneficialin polymer-peroxide master batches (i.e., polymer-peroxide compositionwith up to 5% or more of organic peroxides, useful in crosslinking,curing and polymer modification applications), since the peroxidefunctional groups are compatible with the polymer backbone (covalentlyattached) and cannot bloom, exude or volatilize.

The following illustrative, non-limiting examples are included for thepurpose of further describing and explaining the invention. Example1--Preparation of 4,4-Di-(t-butylperoxy)pentanohydrazide (I-1)

4,4-Di-(t-butylperoxy)pentanohydrazide was prepared by reacting ethyl4,4-di-(t-butylperoxy)pentanoate with 9 molar excess of 54% aqueoushydrazine. A 3-neck flask equipped with a magnetic stirrer, athermometer and an addition funnel was charged with 125 mL ofisopropanol (IPA), 15.3 g (0.05 mole) of 99% ethyl4,4-di-(t-butylperoxy)pentanoate and 30 g (about 0.50 mole) of 54%aqueous hydrazine at 25° C. The solution was stirred for about 20 hoursat 20°-25° C. Then the reaction mass was poured into 1000 mL of waterand extracted once with 300 mL of methylene chloride. After drying over10% by weight of anhydrous magnesium sulfate and separation of the spentdesiccant by filtration, the methylene chloride was removed in vacuoleaving 14.4 g of liquid product. 30 mL of pentane were added and asolid was precipitated. The solid was separated by filtration and airdried, leaving 12.2 g (83.6% of theory, uncorrected) of a white solidhaving a melting point (mp) of 76°-78° C. An infrared (IR) spectrum ofthe product showed strong carbonyl absorption bands at 1640 cm⁻¹ and at1680 cm⁻¹ and a strong NH band at 3300 c⁻¹. A DSC scan run on theproduct showed a peroxide decomposition exotherm at 170° C. Theseproduct data confirm that the product was4,4-Di-(t-butylperoxy)pentanohydrazide (IT1).

In another preparation of 4,4-di-(t-butylperoxy)pentanohydrazide (I-1),46.7 g (0.15 mole) of 98.4% ethyl 4,4-di-(t-butylperoxy)pentanoate and90 g (about 1.50 moles) of 54% aqueous hydrazine in 325 mL of IPA werereacted at 25° C. for about 60 hours. Following the same procedure asdescribed above, 37.4 g (85.4% of theory, uncorrected) of a white solid,mp, 79°-80° C. was obtained. The product had a neutralization equivalentof 294.4 (theory, 292.3) and an active oxygen content of 11.02% (theory,10.95%). Hence, the assay of the product was 100% and the correctedyield was 85.4%. These product data confirm that the product was4,4-di-(t-butylperoxy)pentanohydrazide (I-1).

Example 2--Preparation of 4,4-Di-(t-amylperoxy) pentanohydrazide (I-2)

4,4-Di-(t-amylperoxy)pentanohydrazide was prepared by reacting ethyl4,4-di-(t-amylperoxy)pentanoate with 9 molar excess of 54% aqueoushydrazine in a manner similar to that employed in Example 1 for thepreparation of 4,4-di-(t-butylperoxy)pentanohydrazide. The product,4,4-di-(t-amylperoxy)pentanohydrazide (I-2), had a DSC peroxidedecomposition temperature of 171° C. The yield was 91%. Example3--Preparation of 3,3-Di-(t-butylperoxy)butanohydrazide(I-3)

3,3-Di-(t-butylperoxy)butanohydrazide was prepared by reacting ethyl3,3-di-(t-butylperoxy)butanoate with 9 molar excess of 54% aqueoushydrazine. A 3-neck flask equipped with a magnetic stirrer, athermometer and an addition funnel was charged with 100 mL of IPA, 14.6g (0.05 mole) of 100% ethyl 3,3-di-(t-butylperoxy)butanoate and 30 g(about 0.50 mole) of 54% aqueous hydrazine at 25° C. The solution wasstirred for about 20 hours at 20°-22° C., then the reaction mass waspoured into 1000 mL of water and extracted twice with 200 mL portions ofmethylene chloride. After drying over 10% by weight of anhydrousmagnesium sulfate and separation of the spent desiccant by filtration,the methylene chloride was removed in vacuo leaving 14.3 g (>100% oftheory, uncorrected) of a liquid product. 75 mL of pentane was added,the solution cooled to 0° C. and a solid precipitated. The solid wasseparated by filtration and air dried, leaving 4.8 g (35% of theory,uncorrected) of a white solid, mp, 62°-63° C.

A second preparation of I-3 was carried out in which methyl3,3-di-(t-butylperoxy)butanoate (instead of ethyl3,3-di-[t-butylperoxy]butanoate) was reacted with 9 molar excess of 54%aqueous hydrazine using a procedure similar to the above. A solidproduct (mp, 61°-62° C.) was obtained in an uncorrected yield of 81%.Hence, it appears that the methyl ester reacts more readily andcompletely with hydrazine than does the ethyl ester. The IR spectra ofthe two isolated solid products were identical. A DSC scan run on thelatter prepared product showed a peroxide decomposition exotherm at 176°C. These product data indicate that the products obtained were the samecomposition, 3,3-di-(t-butylperoxy)butanohydrazide (I-3).

Example 4--Preparation of3-(1,4,4,6-Tetramethyl-2,3,7-trioxacycloheptyl)propionhydrazide (I-4)

3-(1,4,4,6-Tetramethyl-2,3,7-trioxacycloheptyl)propionhydrazide wasprepared by reacting3-(ethoxycarbonylethyl)-3,5,7,7-tetramethyl-1,2,4-trioxacycloheptanewith 9 molar excess of 54% aqueous hydrazine.3-(Ethoxycarbonylethyl)-3,5,7,7-tetramethyl-1,2,4-trioxacycloheptane wasinitially prepared in an assay of 89% and a corrected yield of 88% byreacting ethyl levulinate with 10% molar excess of3-hydroxy-1,1-dimethylbutyl hydroperoxide using 70% aqueous sulfuricacid as a catalyst/dehydrating agent.

In the synthesis of the I-4, a 3-neck flask equipped with a magneticstirrer, a thermometer and an addition funnel was charged with 125 mL ofethanol, 14.5 g (0.05 mole) of 89%3-(ethoxycarbonylethyl)-3,5,7,7-tetramethyl-1,2,4-trioxacycloheptane and29.6 g (about 0.50 mole) of 54% aqueous hydrazine at 25° C. The solutionwas stirred for about 20 hours at 20°-25° C. Then the reaction mass waspoured into 300 mL of water containing 0.45 mole of HCl. The pH wasadjusted to 7 by addition of granular sodium carbonate. The solution wasextracted twice with 200 mL portions of methylene chloride and themethylene chloride extractions were combined. After drying over 10% byweight of anhydrous magnesium sulfate and separation of the spentdesiccant by filtration, the methylene chloride was removed in vacuoleaving 8.5 g (69% of theory, uncorrected) of a heavy yellow oil. 25 mLof pentane was added to the liquid product, and after stirring for 5minutes at 25° C. the pentane was decanted off and residual pentane inthe product layer was removed in vacuo leaving 6.6 g (54% of theory,uncorrected) of a heavy yellow oil. An IR spectrum of the product showeda broad carbonyl absorption band centered at 1660 cm⁻¹ and a broad NHband at 3300 cm⁻¹. Also present were small --OO-- bands at 880 cm , 860cm⁻¹ and 840 cm⁻¹. A DSC scan of the product showed a peroxidedecomposition exotherm at 229° C. These product data confirm that theproduct was3-(1,4,4,6-tetramethyl-2,3,7-trioxacycloheptyl)-propionhydrazide I-4.

Example 5--Preparation of 1,3-Dimethyl-3-(t-butylperoxy)butyl Carbazate(I-5)

1,3-Dimethyl-3-(t-butylperoxy)butyl carbazate was prepared by reacting1,3-dimethyl-3-(t-butylperoxy)butyl chloroformate with 11 molar excessof 54% aqueous hydrazine.

A jacketed glass reactor equipped with a mechanical stirrer, athermometer and an addition funnel was charged with 100 mL of methylenechloride and 35.6 g (about 0.60 mole) of 54% aqueous hydrazine at 25° C.The resulting solution was cooled to 0° C. and was vigorously stirredwhile 13.3 g (0.05 mole) of 95% 1,3-dimethyl-3-(t-butylperoxy)butylchloroformate was slowly added over a period of 20 minutes to thestirred solution. The resulting solution was further stirred at 0° C.for 90 minutes, then the solution was poured into 500 mL of water. About35 mL of concentrated aqueous HCl was added to the resulting mixture inorder to bring the pH to 7°-8. Sodium hydrogen carbonate was added tobuffer the mixture at a pH of 8. The methylene chloride layer wasseparated and washed once with 100 mL of water, then dried over 10% byweight of anhydrous magnesium sulfate. After separation of the spentdesiccant by filtration, the methylene chloride was removed in vacuoleaving 14.3 g (>100% of theory, uncorrected) of liquid product. Highperformance liquid chromatography indicated that the purity of theproduct was about 85-90%. An IR spectrum of the product showed a strongcarbonyl absorption band in the region 1710-1720 cm⁻¹ and a strong NHband at 3350 cm⁻¹. A DSC scan of the product showed a peroxidedecomposition exotherm at 192° C. These product data and the method ofsynthesis confirm that the product was1,3-dimethyl-3-(t-butylperoxy)butyl carbazate I-5.

Example 6--Preparation of O-(1,3-Dimethyl-3-[t-butylperoxy]butyl)N-(2-Aminoethyl) Carbamate (I-6)

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-(2-aminoethyl) carbamate wasprepared by reacting 1,3-dimethyl-3-(t-butylperoxy)butyl chloroformatewith 4 molar excess of ethylenediamine.

A jacketed glass reactor equipped with a mechanical stirrer, athermometer and an addition funnel was charged with 100 mL of methylenechloride and 15.0 g (0.25 mole) of ethylenediamine at 25° C. Theresulting solution was vigorously stirred while 13.7 g (0.05 mole) of92.2% 1,3-dimethyl-3-(t-butylperoxy)butyl chloroformate was slowly addedover a period of 30 minutes to the stirred solution. The resultingsolution became cloudy and was further stirred at 25° C. for 30 minutes,then 100 mL of 5% aqueous sodium hydroxide (0.125 mole) was added, themixture stirred 5 minutes, then settled. The aqueous phase was discardedand the methylene chloride solution was washed five (5) times with 100mL portions of water at 20°-25° C. in order to remove any excessethylenediamine. The resulting methylene chloride solution was treatedwith 100 mL of 0.6N hydrochloric acid solution, the aqueous phaseseparated and washed once with 50 mL of methylene chloride. The aqueousphase was then treated with 100 mL of 1.0N sodium hydroxide solution andthe resulting mixture was extracted twice with 75 mL portions ofmethylene chloride. The combined methylene chloride extracts were thenwashed three (3) times with 100 mL portions of water, then dried over10% by weight of anhydrous magnesium sulfate. After separation of thespent desiccant by filtration, the methylene chloride was removed invacuo leaving 11.2 g (81.2% of theory, uncorrected) of a colorlessliquid product.

The product was found to have a neutralization equivalence of 277.3compared to a theoretical neutralization equivalence of 276.3,therefore, the purity of the product appeared to be quite high. An IRspectrum of the product showed a strong carbonyl absorption band in theregion about 1700 cm⁻¹, a strong NH band at 3180 cm⁻¹ and an --OO--absorption band at about 875 cm⁻¹. These product data and the method ofsynthesis confirm that the product wasO-(1,3-dimethyl-3-[t-butylperoxy]butyl) N-(2-aminoethyl) carbamate I-6.Example 7--Preparation of1-(2-Cyano-3,3-diphenylpropenoyl)-Z-(4,4-di-[t-amylperoxy]pentanoyl)hydrazine(I-7)

2-Cyano-3,3-diphenylpropenoyl chloride was initially prepared byreacting 2-cyano-2,2-diphenylpropenoic acid with excess phosgene in thepresence of N,N-dimethylformamide catalyst at about 40° C. Using aprocedure similar to that employed for preparing I-6,1-(2-cyano-3,3-diphenylpropenoyl)-2-(4,4-di-[t-amylperoxy]pentanoyl)hydrazine,I-7, was prepared by reacting 3.2 g. (0.01 mole) of4,4-di-(t-amylperoxy)pentanohydrazide with 2.7 g (0.01 mole) of 100%2-cyano-3,3-diphenylpropenoyl chloride in the presence of 2.0 g (0.026mole) of pyridine and 120 mL of methylene chloride. The reaction mixturewas maintained at 0° C. over a period of about 75 minutes and thenwarmed to room temperature over a period of 60 minutes. Following aprocedure similar to that employed in Example 6, 2.7 g (49% of theory,uncorrected) of light yellow solid having a melting point of 145°-148°C. (gassing) was obtained. An IR spectrum of the product showed an NHband centered at about 3190 cm⁻¹, hydrazide carbonyl bands at 1690 cm⁻¹and 1640 cm⁻¹ and an --OO-- band at about 860 cm⁻¹. A DSC scan of theproduct showed a peroxide decomposition exotherm at 175° C. These IRspectral and DSC product data, as well as the method of preparation,confirm that the product was the desired1-(2-cyano-3,3-diphenylpropenoyl)-2-(4,4-di-[t-amylperoxy]pentanoyl)hydrazine,I-7.

Example 8--Preparation of(2,2,6,6-Tetramethyl-4-piperidinyl)-(4,4-di-[t-butylperoxy]pentanoyl)hydrazone(I-8)

A 100 mL Erlenmeyer flask equipped with an air condenser and a magneticstirring bar was charged with 2.9 g (0.01 mole) of4,4-di-(t-butylperoxy)pentanohydrazide, 60 mL of methanol, 4.0 g (0.049mole) of sodium acetate and 2.3 g (0.012 mole) of2,2,6,6-tetramethyl-4-piperidone hydrochloride. The resulting mixturewas then placed in a heated oil bath, magnetically stirred and refluxed(at about 76° C.) for 4 hours. The mixture was cooled to roomtemperature over about 16 hours. The mixture was then poured into about300 mL of ice water and vigorously stirred. The aqueous solution wasextracted twice with 100 mL portions of methylene chloride. The combinedmethylene chloride extracts were dried over 10% by weight of anhydrousmagnesium sulfate. After separation of the spent desiccant byfiltration, the methylene chloride was removed in vacuo leaving 4.2 g(89% of theory, uncorrected) of a paste. The paste was slurried withabout 20 mL of pentane and the undissolved solid separated by filtrationand air dried, leaving 1.3 g (28% of theory, uncorrected) of whitesolid, mp, 130°-135° C. An IR spectrum of the product showed two NHbands at about 3260 cm⁻¹ and 3190 cm⁻¹, carbonyl bands at 1690 cm⁻¹,1660 cm⁻¹ and 1640 cm⁻¹ and an --OO-- band at about 870 cm⁻¹. A DSC scanof the product showed a peroxide decomposition exotherm at 177° C. TheseIR spectral and DSC product data, as well as the method of preparation,confirm that the product was the desired(2,2,6,6-tetramethyl-4-piperidinyl)-4,4-di-[t-butylperoxy]pentanoyl)hydrazone,I-8.

Example 9--Preparation of1-Benzoyl-2-(4,4-di-[t-butylperoxy]pentanoyl)hydrazine (I-9)

Using a procedure similar to that employed for preparing I-7,1-benzoyl-2-(4,4-di-[t-butylperoxy]-pentanoyl)hydrazine was prepared byreacting 2.9 g (0.01 mole) of 4,4-di-(t-butylperoxy)pentanohydrazidewith 1.6 g (0.011 mole) of 100% benzoyl chloride in the presence of 2.0g (0.026 mole) of pyridine and 100 mL of methylene chloride at 20° C.Following a procedure similar to that employed in Example 7, 2.6 g (65%of theory, uncorrected) of a white solid having a melting point of147°-149° C. was obtained. An IR spectrum of the product showed an NHband centered at about 3230 cm⁻¹, a hydrazide carbonyl band at 1620 cm⁻¹and an --OO-- band at about 880 cm⁻¹. A DSC scan of the product showed aperoxide decomposition exotherm at 177° C. These IR spectral and DSCproduct data, as well as the method of preparation, confirm that theproduct was the desired1-benzoyl-2-(4,4-di-[t-butylperoxy]pentanoyl)hydrazine, I-9.

Example 10-1-(2-Ethylhexoxycarbonyl)-2-(4,4-di-25-[t-butylperoxy]pentanoyl)hydrazine (I-10)

Using a procedure similar to that employed for preparing I-7,1-(2-ethylhexoxycarbonyl)-2-(4,4-di-[t-butylperoxy]pentanoyl)hydrazinewas prepared by reacting 2.9 g (0.01 mole ) of4,4-di-(t-butylperoxy)pentanohydrazide with 2.0 g (0.01 mole) of 99%2-ethylhexyl chloroformate in the presence of 2.0 g (0.026 mole) ofpyridine and 100 mL of methylene chloride at 20° C. Following aprocedure similar to that employed in Example 7, 4.6 g (>100% of theory,uncorrected) of a yellow liquid product was obtained. An IR spectrum ofthe product showed an NH band centered at about 3250 cm⁻¹, carbonylbands at 1720 cm⁻¹ and 1670 cm⁻¹ and an --OO-- band at about 870 cm⁻¹ A.DSC scan of the product showed a peroxide decomposition exotherm at 176°C. These IR spectral and DSC product data, as well as the method ofpreparation, confirm that the product was the desired1-(2-ethylhexoxycarbonyl)-2-(4,4-di-[t-butylperoxy]pentanoyl)hydrazine,I-10.

Example 11--Preparation of 3-Oxapentane-1,5-diylBis(a-[4,4-di-(t-butylperoxy)pentanoyl]carbazate) (I-11)

Using a procedure similar to that employed for preparing of the titlecompound of I-7, 3-oxapentane-1,5-diylbis(2-[4,4-di-(t-butylperoxy)pentanoyl]carbazate) was prepared byreacting 2.9 g (0.01 mole) of 4,4-di-(t-butylperoxy)pentanohydrazidewith 1.16 g (0.005 mole) of 99+% diethylene glycol bis(chloroformate) inthe presence of 2.0 g (0.026 mole) of pyridine and 100 mL of methylenechloride at 20° C. Following a procedure similar to that employed inExample 7, 3.7 g (100% of theory, uncorrected) of a white solid having amelting point of about 45°-50° C. was obtained. An IR spectrum of theproduct showed an NH band centered at about 3250 cm⁻¹, carbonyl bands at1730 cm⁻¹ and 1670 cm⁻¹ and an --OO-- band at about 870 cm⁻¹. A DSC scanof the product showed a peroxide decomposition exotherm at 175° C. TheseIR spectral and DSC product data, as well as the method of preparation,confirm that the product was the desired 3-oxapentane-1,5-diylbis(2-[4,4-di-(t-butylperoxy)pentanoyl]carbazate), I-11.

Example 12--Preparation of 2,2,-Di-(3,3-di-[t-butylperoxy]butanoyl)Dodecanedioic Acid Dihydrazide (I-12).

Using a procedure similar to that employed for preparing I-7,2,2'-di-(3,3-di-[t-butylperoxy]butanoyl) dodecanedioic acid dihydrazidewas prepared by reacting 2.8 g (0.01 mole) of3,3-di-(t-butylperoxy)butanohydrazide with 1.44 g (0.005 mole) of 92.6%1,12-dodecanedioyl dichloride in the presence of 2.0 g (0.026 mole) ofpyridine and 100 mL of methylene chloride at 20° C. Following aprocedure similar to that employed in Example 7, 3.5 g (92% of theory,uncorrected) of a white solid having a melting point of 113°-116° C. wasobtained. An IR spectrum of the product showed an NH band centered atabout 3200 cm⁻, a carbonyl band at about 1610-1620 cm⁻¹ and an --OO--band at about 875 cm⁻¹. A DSC scan of the product showed a peroxidedecomposition exotherm at 181° C. These IR spectral and DSC productdata, as well as the method of preparation, confirm that the product wasthe desired 2,2'-di-(3,3-di-[t-butylperoxy]butanoyl) dodecanedioic aciddihydrazide, I-12.

Example 13--Preparation of N'-(3-Carboxypropionyl)O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) Carbazate (I-13)

N'-(3-Carboxypropionyl) O-(1,3-dimethyl-3-[t-butylperoxy]butyl)carbazate was prepared by reacting 6.9 g (0.025 mole) of1,3-dimethyl-3-(t-butylperoxy)butyl carbazate with 2.6 g (0.026 mole) ofabout 100% succinic anhydride in the presence of 100 mL of methylenechloride at 25° C. Initially, both reactants went into solution. Afterabout 5 minutes, a solid started to precipitate from the solution andthere was a 1°-2° C. rise in temperature. The mixture was furtherstirred for 60 minutes at 25° C. after which the solid was separated byfiltration, washed with methylene chloride and dried. 7.3 g (84% oftheory, uncorrected) of a white solid having a melting point of141°-143° C. was obtained. An IR spectrum of the product showed two NHbands at 3250 cm⁻¹ and 3100 cm⁻¹, a carbazate carbonyl band at about1720 cm⁻¹, a broad carbonyl band at 1680 cm⁻¹ and an --OO-- band atabout 870 cm⁻¹. A DSC scan of the product showed a peroxidedecomposition exotherm at 197° C. These IR spectral and DSC productdata, as well as the method of preparation, confirm that the product wasthe desired N'-(3-carboxypropionyl)O-(1,3-dimethyl-3-[t-butylperoxy]butyl) carbazate, I-13.

Example 14--Preparation of3-(1,4,4,6-Tetramethyl-2,3,7-trioxacycloheptyl)-N'-(3-carboxypropionyl)propionhydrazide(I-14)

3-(1,4,4,6-Tetramethyl-2,3,7-trioxacycloheptyl)-N'-(3-carboxypropionyl)propionhydrazidewas prepared by reacting 1.2 g (0.0044 mole) of3-(1,4,4,6-tetramethyl-2,3,7-trioxacycloheptyl)propionhydrazide with 0.5g (0.0050 mole) of about 100% succinic anhydride in the presence of 30mL of methylene chloride at 25° C. Initially, both reactants went intosolution and no precipitation occurred during 120 minutes at 25° C. Then100 mL of pentans was added to the solution and a solid began toprecipitate. The mixture was stirred for an additional 30 minutes at 25°C., then the solid was separated by filtration, washed with pentans anddried. 1.2 g (80% of theory, uncorrected) of a white solid having amelting point of 122°-126° C. was obtained. An IR spectrum of theproduct showed two NH bands at 3240 cm⁻¹ and 3100 cm⁻¹, a hydrazidecarbonyl band at about 1706 cm⁻¹, an acid carbonyl band at 1675 cm⁻¹ anda small --OO-- band at about 900 cm⁻¹. A DSC scan of the product showeda peroxide decomposition exotherm at 226° C. These IR spectral and DSCproduct data, as well as the method of preparation, confirm that theproduct was the desired3-(1,4,4,6-tetramethyl-2,3,7-trioxacycloheptyl)-N'-(3-carboxypropionyl)propionhydrazide,I-14.

Example 15--Preparation of a Polymeric Peroxide (I-15) via Reaction of1,3-Dimethyl-3-(t-butylperoxy)butyl Carbazate (I-5) with aPoly(styrene-co-maleic anhydride) Copolymer

In this example, a poly(styrene-co-maleic anhydride) copolymer, Dylark™232 (Arco), containing about 9% by weight of maleic anhydride (MA)units, was reacted with 1,3-dimethyl-3-(t-butylperoxy)butyl carbazate(I-5) to form a poly(styrene-co-maleamic acid) copolymer possessingpendant peroxide groups.

A 125 mL Erlenmeyer flask equipped with a magnetic stirring bar wascharged with 10 g of Dylark™ 232 -poly(styrene-Co-maleic anhydride)copolymer (0.0092 mole of MA units) and 50 g of toluene and the mixturewas stirred and heated to 80°-90° C. in order to dissolve the polymer.Then 2.1 g (0.0076 mole) of 1,3-dimethyl-3-(t-butylperoxy)butylcarbazate (I-5) in 20 g of toluene was rapidly added to the toluenesolution of Dylark™ 232 and the resulting solution was allowed to coolfrom 85° C. to 35° C. over a period of 150 minutes. The solution wasthen added to 500 mL of vigorously stirred methanol in a stainless steelWaring blender in order to precipitate the polymer. The solid polymerwas washed twice at room temperature with 500 mL portions of vigorouslystirred methanol in the Waring blender in order to remove unreacted I-5and other impurities from the polymer. The polymer was then dried. 10.7g (theoretical yield=11.9 g; 90% of theory, uncorrected) of whitegranular polymer was obtained. A DSC scan of the product showed aperoxide decomposition exotherm at 208° C. It should be noted that I-5had a peroxide decomposition temperature of 197° C. (see Example 5).Based on the DSC data, the method of preparation and the method ofisolation, the polymeric product produced in this example is confirmedas being a poly(styrene-co-maleamic acid) copolymer possessing pendantperoxide groups. Furthermore, the pendant peroxide groups have the1,3-dimethyl-3-(t-butylperoxy)butyl carbazate (I-5) structure. Thus,I-15 was produced.

Example 16--Preparation of a Polymeric Peroxide (I-16) via Reaction of3,3-Di-(t-butylperoxy)butanohydrazide (I-3) with aPoly(1-octadecene-co-maleic anhydride) Copolymer

In this example, a poly(1-octadecene-co-maleic anhydride) alternatingcopolymer, PA-18™ (Gulf), containing about 29% by weight of MA units,was reacted with 3,3'-di-(t-butylperoxy)butanohydrazide (I-3) to form apoly(1-octadecene-co-maleamic acid) copolymer possessing pendantperoxide groups.

A 50 mL Erlenmeyer flask equipped with a magnetic stirring bar wascharged with 1.00 g of Gulf's PA-18™ poly(1-octadecene-co-maleicanhydride) alternating copolymer (0.0029 mole of MA units), 0.56 g(0.0020 mole) of 3,3-di-(t-butylperoxy)butanohydrazide (I-3) and 10 g oftoluene. The mixture was stirred and heated at 50° C. for 30 minutes. AnIR spectrum of the solution showed that the anhydride absorption bandsat 1770 cm⁻¹ and at 1850 cm⁻¹ for the starting PA-18 copolymer weresignificantly diminished as was the NH band at about 3300 cm⁻¹ for thestarting hydrazine (I-3). The strong amide carbonyl band at 1640 cm⁻¹for the starting hydrazine (I-3) was also gone. A new, strong amic acidcarbonyl band at 1700 cm⁻¹ was observed for the product solution. Basedon the IR data and method of preparation the polymeric product producedin this example is confirmed as being a poly(1-octadecene-co-maleamicacid) copolymer possessing pendant peroxide groups. Furthermore, thependant peroxide groups have the 3,3-di-(t-butylperoxy)butanohydrazide(I-3) structure. Thus, the I-16 copolymer was produced.

Example 17--Preparation of a Polymeric Peroxide

(I-17) via Reaction of O-(1,3-Dimethyl-3-[t-butylperoxy]butyl)N-(2-Aminoethyl) Carbamate (I-6) with a Poly(1-octadecene-co-maleicanhydride) Copolymer

In this example a poly(1-octadecene-co-maleic anhydride) alternatingcopolymer, PA-18™ (Gulf), containing about 29% by weight of MA units,was reacted with O-(1,3-dimethyl-3-[t-butylperoxy]butyl)N-(2-aminoethyl) carbamate (I-6) to form a poly(1-octadecene-co-maleamicacid) copolymer possessing pendant peroxide groups.

A 125 mL Erlenmeyer flask equipped with a magnetic stirring bar wascharged with 28.0 g of a toluene solution containing 7.0 g of Gulf'sPA-18 poly(1-octadecene-co-maleic anhydride) alternating copolymer(0.0200 mole of MA units) and 4.6 g (0.0166 mole) ofO-(1,3-dimethyl-3-[t-butylperoxy]butyl) N-(2-aminoethyl) carbamate (I-6)at room temperature. The mixture was stirred and heated to and held at55° C. for 300 minutes. An IR spectrum of the PA-18 solution showedanhydride carbonyl absorption bands at 1775 cm⁻¹ and at 1855 cm⁻¹ and a5-membered cyclic anhydride stretching absorption band at about 925cm⁻¹. An IR spectrum of the product solution showed that the anhydrideabsorption bands at 1775 cm⁻¹ and at 1855 cm⁻¹ were significantlydiminished. In addition, the 5-membered cyclic anhydride stretchingabsorption band at about 925 cm⁻¹ was nearly gone in the productsolution. Furthermore, an amide carbonyl band was present at about 1700cm⁻¹ and an --OO-- band was present at about 870 cm⁻¹ in the productsolution. The product solution became extremely viscous which wasconsistent with the formation of a poly(amic acid) solution (owing toformation of a hydrogen bond network). Based on the IR data, the methodof preparation and the solution properties, the polymeric productproduced in this example is confirmed as being apoly(1-octadecene-co-maleamic acid) copolymer possessing pendantperoxide groups. Furthermore, the pendant peroxide groups have theO-(1,3-dimethyl-3-[t-butylperoxy]butyl) N-(2-aminoethyl) carbamate (I-6)structure. Thus, the I-17 copolymer was produced.

Example 18--138° C. SPI Exotherms of4,4-Di-t-butylperoxy)pentanohydrazide (I-1)

The unsaturated polyester resin composition employed in this example wasa mixture of an unsaturated polyester and styrene monomer. Theunsaturated polyester was an alkyd resin made by esterifying thefollowing components:

    ______________________________________                                        Component (moles)                                                                              Quantity                                                     ______________________________________                                        Maleic Anhydride 1.0                                                          Phthalic Anhydride                                                                             1.0                                                          Propylene Glycol 2.2                                                          ______________________________________                                    

0.013% by weight of hydroquinone inhibitor was added to the resultingresin. The alkyd resin had an Acid No. of 45-50. Seven (7) parts byweight of the above unsaturated polyester alkyd were diluted with three(3) parts by weight of monomeric styrene. The resulting unsaturatedpolyester resin composition had the following properties:

a. Viscosity (Brookfield No. 2 at 20 r.p.m.): 13.0 -poise

b. Specific gravity: 1.14

Gelation and cure characteristics of ethyl3,3-di-(t-butylperoxy)butanoate (A-1), a well known curing catalyst forunsaturated polyester resin compositions, and4,4-di-(t-butylperoxy)pentanohydrazide (I-1), a composition of thepresent invention, were determined using the Standard SPI ExothermProcedure ("SPI Procedure for Running Exotherm Curves-Polyester Resins,"published in the Preprint of the 16th Annual Conference-ReinforcedPlastics Division, Society of the Plastics Industry, Inc., February,1961). Using the procedure at 138° C. (280° F.), A-1 and I-1 wereevaluated.

The results are summarized in Table 18-1 and show that I-1, acomposition of the present invention, is surprisingly active in gellingand curing the unsaturated polyester resin. This is a surprising resultin that the hydrazine group of I-1 would be expected to react with freeradicals and adversely affect the curing. The use of I-1 with itshydrazine functionality not only did not adversely affect the cure, itenhanced the cure as indicated by the substantially faster curing time.

                  TABLE 18-1                                                      ______________________________________                                        SPI Exotherm Data at 138° C.                                           Curing Level,   Gel,    Cure,  Peak Exo-                                                                             Barcol                                 Catalyst                                                                             %        mins    mins   therm, °F.                                                                     Hardness                               ______________________________________                                        A-1    1.0      2.2     2.8    445     45-50                                  I-1    1.0      1.0     2.2    400     45-50                                  ______________________________________                                    

Example 19--Preparation of 1,3-Dimethyl-3-(2-ethylhexanoylperoxy)butylCarbazate (I-19)

1,3-Dimethyl-3-(a-ethylhexanoylperoxy)butyl carbazate was prepared byreacting 1,3-dimethyl-3-(2-ethylhexanoylperoxy)butyl chloroformate with11 molar excess of 54% aqueous hydrazine.1,3-Dimethyl-3-(2-ethylhexanoylperoxy)butyl chloroformate was initiallyprepared with a purity of 72% by reacting 3-hydroxy-1,1-dimethylbutylperoxy-2-ethylhexanoate with excess phosgene followed by removal ofexcess phosgene.

A jacketed glass reactor equipped with a mechanical stirrer, athermometer and an addition funnel was charged with 80 mL of methylenechloride and 23.1 g (about 0.39 mole) of 54% aqueous hydrazine at 25° C.The resulting solution was cooled to 0° C. and was vigorously stirredwhile 15.7 g (0.035 mole) of 72%1,3-dimethyl-3-(2-ethylhexanoylperoxy)butyl chloroformate in 20 mL ofmethylene chloride was slowly added over a period of 20 minutes to thestirred solution at 0°-5° C. The resulting solution was further stirredat 0°-5° C. for 120 minutes. The resulting solution was then washed sixtimes with 50 mL portions of water and the methylene chloride solutionwas dried over 10% by weight of anhydrous magnesium sulfate. Afterseparation of the spent desiccant by filtration, the methylene chloridewas removed in vacuo leaving 11.3 g (>100% of theory, uncorrected) ofyellow liquid product. An IR spectrum of the product showed strongcarbonyl absorption bands at 1770 cm⁻¹, 1720 cm⁻¹ and 1650 cm⁻¹ (amidecarbonyl) and a strong NH band at 3350 cm⁻¹. A DSC scan of the productshowed a peroxide decomposition exotherm at 130° C. These product dataand the method of synthesis confirm that the product was1,3-dimethyl-3-(2-ethylhexanoylperoxy)butyl carbazate, I-19.

Example 20--Preparation ofO-(1,3-Dimethyl-3-[2-ethylhexanoylperoxy]butyl)N'-(1,3-Dimethyl-3-[t-butylperoxy]butoxycarbonyl) Carbazate (I-20)

Preparation of O-(1,3-dimethyl-3-[2-ethylhexanoylperoxy]butyl)N'-(1,3-dimethyl-3-[t-butylperoxy]butoxycarbonyl) carbazate, asequential peroxide, was prepared by reacting equal molar amounts of1,3-dimethyl-3-(2-ethylhexanoylperoxy)butyl chloroformate and1,3-dimethyl-3-(t-butylperoxy)butyl carbazate (I-5) in the presence ofexcess pyridine.

A three-neck flask equipped with a magnetic stirring bar, a thermometer,a condenser and an addition funnel was charged with 80 mL of methylenechloride, 2.0 g (0.026 mole) of pyridine and 2.7 g (0.010 mole) of1,3-dimethyl-3-(t-butylperoxy)butyl carbazate (I-5). This solution wasstirred at 20°-25° C. and a solution of 4.5 g (0.010 mole) of 72%1,3-dimethyl-3-(2-ethylhexanoylperoxy)butyl chloroformate in 20 mL ofmethylene chloride was slowly added to it. A very slight exotherm wasnoted. The reaction mixture was stirred for 4 hours at 25° C. afterwhich it was washed with two 25 mL portions of 5% aqueous sulfuric acidsolution, followed by three 50 mL water washes. The methylene chloridesolution was then dried over 10% by weight of anhydrous magnesiumsulfate. After separation of the spent desiccant by filtration, themethylene chloride was removed in vacuo leaving 5.1 g (96% of theory,uncorrected) of a straw-colored liquid product. An IR spectrum of theproduct showed a strong carbonyl absorption band at 1730 cm⁻¹ and astrong NH band at 3360 cm⁻¹. A DSC scan of the product showed, asexpected, two peroxide decomposition exotherms, one at about 125° C. andthe other at about 185° C. These product data and the method ofsynthesis confirm that the product wasO-(1,3-dimethyl-3-[2-ethylhexanoylperoxy]butyl)N'-(1,3-dimethyl-3-[t-butylperoxy]butoxycarbonyl) carbazate, I-20.

Example 21--Preparation ofO-(1,3-Dimethyl-3-[t-butylperoxy]butyl)N-Succinimido Carbamate (I-21)

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-succinimido carbamate wasprepared by reacting N'-(3-carboxypropionyl)1,3-dimethyl-3-(t-butylperoxy)butyl carbazate (I-13) with aceticanhydride and sodium acetate.

A 3-neck flask equipped with a magnetic stirrer, a thermometer and areflux condenser was charged with 7.0 g (0.020 mole) ofN'-(3-carboxypropionyl) 1,3-dimethyl-3-(t-butylperoxy)butyl carbazate(I-13, 100% assay assumed), 1.3 g (0.016 mole) of sodium acetate and20.4 g (0.200 mole) of acetic anhydride at room temperature. Thereaction mass was stirred, heated to and held at 75° C. for 10-15minutes. The starting peroxide went into solution. The reaction mass wasthen cooled to room temperature, then poured into 200 mL of water,stirred for 30 minutes at room temperature and extracted twice with 75mL portions of methylene chloride. The combined methylene chlorideextracts were then washed at room temperature twice with 100 mL portionsof water, then twice with 80 mL portions of 8% aqueous NaHCO₃ solution.The methylene chloride solution was then dried over 10% by weight ofanhydrous magnesium sulfate. After separation of the spent desiccant byfiltration, the methylene chloride was removed in vacuo, leaving 6.7 g(100% of theory, uncorrected) of a viscous colorless liquid product. Theproduct was then dissolved in pentane and over a period of several hoursa solid precipitated from solution. The white solid was separated byfiltration, washed with fresh pentane and dried. 2.5 g (38% of theory,uncorrected) of a white solid having a melting point of 79°-83° C. wasobtained. An IR spectrum of the product showed an NH band (sharp) at3300 cm⁻¹, a small imide carbonyl band at 1790 cm⁻¹, a strong imidecarbonyl band at 1720 cm⁻¹ and a small -- OO-- band at about 875 cm⁻¹. ADSC scan of the product showed a peroxide decomposition exotherm atabout 195° C. IR spectral and DSC data and the method of synthesisconfirm that the product was O-(1,3-dimethyl-3-[t-butylperoxy]butyl)N-succinimido carbamate, I-21, the desired product.

Example 22--Preparation ofO-(1,3-Dimethyl-3-[t-butylperoxy]butyl)N-Maleimido Carbamate (I-22)

O-(1,3-Dimethyl-3-[t-butylperoxy]butyl) N-maleimido carbamate wasprepared by reacting 1,3-dimethyl-3-(t-butylperoxy)butyl carbazate (I-5)with maleic anhydride to form theO-(1,3-dimethyl-3-[t-butylperoxy]butyl) N'-(cis-3carboxypropenoyl)carbazate intermediate, followed by subsequent treatment with aceticanhydride and sodium acetate.

A 3-neck flask equipped with a magnetic stirrer, a thermometer and areflux condenser was charged with 100 mL of methylene chloride, 2.5 g(0.026 mole) of maleic anhydride and 6.9 g (about 90% pure; 0.025 mole)of 1,3-dimethyl-3-(t-butylperoxy)butyl carbazate (I-5). The solution wasstirred for 60 minutes at room temperature. No solid formed. Theresulting solution was stripped of solvent, leaving 9.3 g of glassyproduct. This was assumed to be the maleamic acid intermediate,O-(1,3-dimethyl-3-[t-butylperoxy]butyl) N'-(cis-3carboxypropenoyl)carbazate.

The intermediate was then treated with 5.5 g (0.250 mole) of aceticanhydride and 1.7 g (0.021 mole) of sodium acetate and transferred to a3-neck flask equipped with a magnetic stirrer, a thermometer and areflux condenser. The mixture was stirred, heated to and held at 70°-80°C. for 11 minutes. During the stir period at 70°-80° C., theintermediate became less viscous, indicating that the desired productwas forming. The resulting reaction mixture was then poured into 300 mLof water, stirred for 30 minutes at room temperature and extracted twicewith 75 mL portions of methylene chloride. The combined methylenechloride extracts were then washed twice at room temperature with 100 mLportions of water. The methylene chloride solution was then dried over10% by weight of anhydrous magnesium sulfate. After separation of thespent desiccant by filtration, the methylene chloride was removed invacuo leaving 9.3 g (>100% of theory, uncorrected) of a yellow, lowviscosity liquid which had a strong odor.

The product was dissolved in 100 mL of methylene chloride and themethylene chloride solution was washed twice with 90 mL portions of 3%aqueous NaOH solution. The aqueous layers became yellow. The methylenechloride solution was then dried over 10% by weight of anhydrousmagnesium sulfate, and, after separation of the spent desiccant byfiltration, the methylene chloride was removed in vacuo, leaving 3.0 g(37% of theory, uncorrected) of a slushy solid. 30 mL of pentane wasadded and the white solid was separated by filtration, washed with freshpentane and dried to give 1.4 g (17% of theory, uncorrected) of whitesolid having a melting point of 94°-97° C. An IR spectrum of the productshowed an NH band at about 3360 cm⁻¹, a small imide carbonyl band at1790 cm⁻¹, a strong imide carbonyl band at 1730 cm⁻¹ and a small --OO--band at about 865 cm⁻¹. Also present in the IR spectrum was a weak C═Cband at about 1640 cm. A DSC scan of the product showed a peroxidedecomposition exotherm at about 195° C. IR spectral and DSC data and themethod of synthesis confirm that the product wasO-(1,3-dimethyl-3-[t-butylperoxy]butyl) N-maleimido carbamate, I-22, thedesired product.

Example 23--Preparation of a poly(1-octadecene-co-maleamic acid)Copolymer Possessing Pendant Peroxide Groups (I-23) via Reaction of1,3-Dimethyl-3-(t-butylperoxy)butyl Carbazate (I-5) with aPoly(1-octadecene-co-maleic anhydride) Copolymer

In this example a poly(1-octadecene-co-maleic anhydride) alternatingcopolymer, PA-18™ (Gulf), containing about 29% by weight of MA units,was reacted with 1,3-dimethyl-3-(t-butylperoxy)butyl carbazate (I-5) toform a poly(1-octadecene-co-maleamic acid) copolymer possessing pendantperoxide groups (I-23).

A 125 mL Erlenmeyer flask equipped with a magnetic stirring bar and athermometer was charged with 28.0 g of a toluene solution containing 7.0g of Gulf's PA-18™ poly(1-octadecene-co-maleic anhydride) alternatingcopolymer (0.020 mole of MA units) and 6.0 g (0.022 mole) of1,3-dimethyl-3-(t-butylperoxy)butyl carbazate (I-5) at room temperature.The mixture was stirred, heated to and held at 95° C. for 240 minutes.An initial IR spectrum of the PA-18™ solution showed anhydride carbonylabsorption bands at 1780 cm⁻¹ and at 1855 cm⁻¹ and a 5-membered cyclicanhydride stretching absorption band at about 925 cm⁻¹. An IR spectrumof the product solution after 240 minutes at 95° C. showed that theanhydride absorption bands at 1780 cm⁻¹ and at 1855 cm⁻¹ wereessentially gone. In addition, the 5-membered cyclic anhydridestretching absorption band at about 925 cm⁻¹ was nearly gone in theproduct solution. Furthermore, an amide carbonyl band was present atabout 1720 cm⁻¹ and an --OO-- band was present at about 870 cm⁻¹ in theproduct solution. The product solution became extremely viscous whichwas consistent with the formation of a poly(maleamic acid) solution(owing to formation of a hydrogen bond network).

The product solution was poured into a shallow glass bake pan and placedin a hood in order to volatilize the toluene. After three days, abrittle polymer film formed in the bottom of the bake pan. The film wasbroken up with a metal spatula, then the resulting polymer was washedthree times with 100 mL portions of methanol in order to removeunreacted 1,3-dimethyl-3-(t-butylperoxy)butyl carbazate, I-5. (I-5 wasfound to be completely miscible with methanol.) The methanol-swollenpolymer was then allowed to dry over a period of two days. The methanolextracts were combined and the methanol was allowed to evaporate over aperiod of two days at room temperature. About 0.5 g of a yellow liquidwas obtained which was identified as 1,3-dimethyl-3-(t-butylperoxy)butylcarbazate, I-5. The dried polymer obtained after two days of drying wascrushed to form 9.0 g (75% of theory, uncorrected) of light yellowpowder. An IR spectrum of the resin product as a Nujol mull showed acarboxylic acid OH band at about 3500 cm⁻¹, an NH band at about 3280cm⁻¹, an amide carbonyl band at about 1720 cm⁻¹ and an --OO-- band atabout 870 cm⁻¹. A DSC scan run on the product showed a peroxidedecomposition exotherm at about 195° C.

Based on the IR data, the method of preparation, the DSC decompositiondata and solution properties, the polymeric product produced in thisexample is confirmed as being a poly(1-octadecene-co-maleamic acid)copolymer possessing pendant peroxide groups, I-23. Furthermore, thependant peroxide groups have the 1,3-dimethyl-3-(t-butylperoxy)butylcarbazate (I-5) structure.

Example 24--Conversion of a Poly(1-octadecene-co-maleamic acid)Copolymer Possessing Pendant Peroxide Groups (I-23) to a Poly(1-octadecene-co-maleimide) Copolymer Possessing Pendant Peroxide Groups(I-24) via Reaction with Aceticanhydride and Sodium Acetate.

In this example a poly(1-octadecene-co-maleamic acid) copolymerpossessing pendant peroxide groups, I-23, was treated with aceticanhydride and sodium acetate to form the desired poly(1-octadecene-co-maleimide) copolymer possessing pendant peroxidegroups, I-24.

A 3-neck flask equipped with a magnetic stirring bar and a thermometerwas charged with 100 mL toluene, 8.0 g (13.37 mmoles of maleamic acidunits) of poly(1-octadecene-co-maleamic acid) copolymer possessingpendant peroxide groups, I-23, 1.3 g (0.016 mole) of sodium acetate and20.4 g (0.200 mole) of acetic anhydride. The resulting mixture wasstirred, then heated to and held at 85°-95° C. for 60 minutes. Themixture was then cooled to room temperature and was subsequently washedfour times with hot (45°-50° C.) water over periods of 10 minutes. Theresulting toluene solution was then dried over 10% by weight ofanhydrous magnesium sulfate, and, after separation of the spentdesiccant by filtration, the product solution was poured into a shallowglass bake pan and placed in a hood in order to volatilize the toluene.After five days a sticky polymer film formed in the bottom of the bakepan. The resulting resin no longer had the odor of toluene.

The film was broken up with a metal spatula and 6.0 g (77% of theory,uncorrected) of rubbery resin were obtained. In addition, whereas theproduct resin was soluble in hexane, the starting resin, I-23, was not.A dry film of the product resin was cast onto an NaCl IR plate and an IRspectrum was obtained. A small NH band at about 330 cm⁻¹, an imidecarbonyl band at about 1730 cm⁻¹ and an --OO-- band at about 870 cm⁻¹were observed. A dry film of starting poly(1-octadecene-co-maleamicacid) copolymer possessing pendant peroxide groups, I-23, was cast ontoan NaCl IR plate from a toluene solution. An IR spectrum was observedthat was significantly different than that of the product resin. Presentwere a broad carboxylic acid OH band at about 3500 cm⁻¹, a broad andstrong NH band at about 3290 cm⁻¹, a broad carbonyl band centered about1720 cm⁻¹ with prominent shoulders at about 1850 cm⁻¹, 1780 cm⁻¹ and1650 cm⁻¹ and an --OO-- band at about 870 cm⁻¹. A DSC scan of theproduct resin showed a peroxide decomposition exotherm at 197° C.

Based on the IR data, the method of preparation, the DSC decompositiondata and solution properties the polymeric product produced in thisexample is the desired poly(1-octadecene-co-maleimide) copolymerpossessing pendant peroxide groups, I-24. Furthermore, the pendantperoxide groups have the 1,3-dimethyl-3-(t-butylperoxy)butyl carbazate(I-5) structure.

The present invention may be embodied in other specific forms withoutdeparting from the spirit or essential attributes thereof and,accordingly, reference should be made to the appended claims, ratherthan to the foregoing specification as indicating the scope of theinvention.

I claim:
 1. An improved process selected from the group consistingof:(a) a process for the initiation of polymerization of ethylenicallyunsaturated monomers by reacting the monomers with an initiatingcompound under conditions effective to initiate polymerization of themonomers; (b) a process for curing an elastomeric resin by reacting theresin with an initiating amount of a free radical initiator for polymercuring under conditions effective to cure the elastomeric resin; (c) aprocess for modifying a polymer selected from the group consisting ofpolypropylene and copolymers comprising more than 50% by weight ofpolypropylene, by varying the molecular weight and modifying themolecular weight distribution of the polymer by reacting said polymerwith an initiating amount of a free radical initiator for polymermodification under conditions effective to modify the polymers, and (d)a process for crosslinking olefin polymers by reacting said olefinpolymers with an initiating amount of a free radical initiator forpolymer crosslinking under conditions effective to crosslink saidpolymers, wherein the improvement consists of the use as the freeradical initiator a compound of structure A: ##STR19## where x is 0 or1, y is 1 or 2 and z is 1 to 3, with the further provisos that when y is2, z can only be 1 and when z is 2 or 3, y can only be 1, and (I) when yis 1 and z is 1, P is a peroxide-containing mono-radical having astructure: ##STR20## where w is 1 or 2; R is a substituted orunsubstituted t-alkyl radical of 4 to 12 carbons, a substituted orunsubstituted t-aralkyl radical of 9 to 13 carbons, a t-cycloalkylradical of 5 to 12 carbons or a substituted or unsubstituted t-alkynylradical of 5 to 10 carbons; R1 is a substituted or unsubstituted,branched or unbranched, alkyl radical of 1 to 13 carbons, a substitutedor unsubstituted cycloalkyl radical of 5 to 10 carbons, a substituted orunsubstituted, branched or unbranched, aralkyl radical of 7 to 11carbons or a substituted or unsubstituted aryl radical of 6 to 10carbons; R1' is a substituted or unsubstituted, branched or unbranchedalkyl radical of 1 to 13 carbons, a substituted or unsubstitutedcycloalkyl radical of 5 to 10 carbons or a substituted or unsubstituted,branched or unbranched, aralkyl radical of 7 to 11 carbons; R2 and R3are the same or different and are substituted or unsubstituted alkylradicals of 1 to 4 carbons; the substituents for R, R1, R1', R2 and R3being alkyl radicals of 1 to 4 carbons, chloro or bromo; R4 is hydrogen,a substituted or unsubstituted alkyl radical of 1 to 10 carbons or asubstituted or unsubstituted aryl radical of 6 to 10 carbons, the R4substituents being one or more alkyl radicals of 1 to 8 carbons, chloro,bromo or carboxy; T is nothing or --O--; R11 is a substituted orunsubstituted alkylene diradical of 2 to 8 carbons or a substituted orunsubstituted 1,2-, 1,3- or 1,4-phenylene diradical, the R11substituents being alkyl radicals of 1 to 4 carbons, chloro or bromo; Xis nothing, ##STR21## R22 is a substituted or unsubstituted alkylenediradical of 2 to 10 carbons or a substituted or unsubstituted 1,2-,1,3- or 1,4-phenylene diradical, the R22 substituents being alkylradicals of 1 to 3 carbons, chloro or bromo, with the proviso that R22can also be nothing when x is 1; Q is a nitrogen-containing radicalhaving a nitrogen-containing structure (a), (b), (c), (d) or (e), or arecurring unit in an addition polymer of ethylenic monomers having astructure (f) or (g): ##STR22## where R33 is a substituted orunsubstituted 1,2- or 1,3- alkylene diradical of 2 to 18 carbons, asubstituted or unsubstituted 1,2- or 1,3-alkenylene diradical of 2 to 18carbons, a substituted or unsubstituted 1,2-cycloalkylene diradical of 5to 6 carbons, a substituted or unsubstituted 1,2-cycloalkenylenediradical of 5 to 6 carbons, a substituted or unsubstituted1,2-bicycloalkylene diradical of 7 to 9 carbons, a substituted orunsubstituted 1,2-bicycloalkenylene diradical of 7 to 9 carbons, asubstituted or unsubstituted 1,2-phenylene diradical, a substituted orunsubstituted 1,2-naphthenylene diradical, a substituted orunsubstituted 2,3-naphthenylene diradical or a substituted orunsubstituted 1,8-naphthenylene diradical, the R33 substituents beingone or more alkyl radicals of 1 to 8 carbons, chloro, bromo, nitro,carboxy, alkoxy radicals of 1 to 8 carbons or alkoxycarbonyl radicals of2 to 9 carbons; R33' is a substituted or unsubstituted 1,2-phenylenediradical, the R33' substituents being one or more alkyl radicals of 1to 8 carbons, chloro, bromo; A⁻ is chloride, bromide, sulfate, acidsulfate, phosphate, acid phosphate, p-methylphenylsulfonate,phenylsulfonate, methylsulfonate, phenylphosphonate,cyclohexylphosphonate or carboxylate from any carboxylic acid; R5 ishydrogen, a substituted or unsubstituted acyl radical of 1 to 18carbons, a substituted or unsubstituted alkenoyl radical of 3 to 10carbons, a perfluoroacyl radical of 2 to 18 carbons, a substituted orunsubstituted aroyl radical of 7 to 11 carbons, a substituted orunsubstituted cycloalkylcarbonyl radical of 6 to 13 carbons, asubstituted or unsubstituted cycloalkenylcarbonyl radical of 6 to 13carbons, a substituted or unsubstituted bicycloalkylcarbonyl radical of6 to 13 carbons, a substituted or unsubstituted alkoxycarbonyl radicalof 2 to 19 carbons, a substituted or unsubstituted alkenyloxycarbonylradical of 3 to 8 carbons, a substituted or unsubstitutedaryloxycarbonyl radical of 7 to 11 carbons, a substituted orunsubstituted cycloalkoxycarbonyl radical of 6 to 13 carbons, asubstituted or unsubstituted alkylaminocarbonyl radical of 2 to 19carbons, a substituted or unsubstituted alkenylaminocarbonyl radical of3 to 8 carbons, a substituted or unsubstituted arylaminocarbonyl radicalof 7 to 11 carbons, an alkylsulfonyl radical of 1 to 8 carbons, or asubstituted or unsubstituted arylsulfonyl radical of 6 to 10 carbons;the R5 substituents being one or more alkyl radicals of 1 to 8 carbons,chloro, bromo, nitro, carboxyl, alkoxy radicals of 1 to 8 carbons oralkoxycarbonyl radicals of 2 to 9 carbons, with the proviso that whenR22 is nothing, the R5 substituents can additionally be at-alkylperoxycarbonyl radical of 5 to 9 carbons, at-alkylperoxycarbonyloxy radical of 5 to 9 carbons or a t-alkylperoxyradical of 4 to 8 carbons; R8 is a substituted or unsubstitutedalkylidene diradical of 2 to 12 carbons, a substituted or unsubstitutedcycloalklidene diradical of 5 to 12 carbons, optionally possessing asone or more heteroatoms N, O or S in the cycloalkylidene chain, or asubstituted or unsubstituted benzylidene diradical of 7 to 11 carbons,the R8 substituents being one or more alkyl radicals of 1 to 8 carbons,chloro, bromo, carboxy or nitro; the recurring unit in polymer structure(f) and (g) being, respectively: ##STR23## in which the recurring units(f) or (g) occur in the polymer backbone or as pendant units orboth,where Ri and Rii are the same or different and are hydrogen, analkyl radical of 1 to 6 carbons, a cycloalkyl radical of 5 to 7 carbons,phenyl, chloro or bromo; t is 0 or 1; and G shows the point ofattachment of group Q to the residue of Structure A; (II) when y is 1and z is 2, P is a peroxide-containing diradical having a structure:##STR24## where R55 is an alkylene diradical of 1 to 6 carbons, analkynylene diradical of 2 to 6 carbons, an alkadiynylene diradical of 4to 8 carbons or a 1,3- or 1,4-phenylene diradical; and R11, X, R22, Q,R2, R3 and x are the same as when y is 1 and z is 1, with the provisothat Q cannot be the above-defined recurring unit (f) or (g) in apolymer; (III) when y is 1 and z is 3, P is a peroxide-containingtri-radical having a structure: ##STR25## where R11, X, R22, Q, R2, R3and x are the same as when y is 1 and z is 1, with the proviso that Qcannot be the above-defined recurring unit in a polymer; and (IV) when zis 1 and y is 2, P, R11 and X are the same as when y is 1 and z is 1;R22 is nothing; and Q is a nitrogen-containing diradical having astructure (m), (n) or (o); ##STR26## where R5' is --SO₂ --, ##STR27##R66 is nothing or a diradical having a structure:

    --R77--,

    --Y--R77--Y--,

    --R77--Z--R77--

or

    --Y--R77--Z--R77--7--,

where Y is --NH--, --S-- or --O--; R77 is a substituted or unsubstitutedalkylene diradical of 2 to 10 carbons, optionally having one or more--O-- or --S-- heteroatoms in the alkylene chain, or a substituted orunsubstituted 1,2-, 1,3- or 1,4-phenylene diradical, the R77substituents being one or more alkyl radicals of 1 to 8 carbons, chloro,bromo, carboxy, nitro or alkoxy radicals of 1 to 8 carbons; Z is nothingor a substituted or unsubstituted alkylene diradical of 1 to 8 carbonsor a diradical having a structure: ##STR28## where R9 and R9' are thesame or different and are hydrogen or alkyl radicals of 1 to 10 carbons,and R9 and R9' can be connected together to form a carbocyclic ringcontaining 5 to 12 carbons and having substituents of one or more alkylradicals of 1 to 4 carbons; and R88 is a substituted or unsubstitutedalkylene diradical of 2 to 10 carbons, the R88 substituents being alkylradicals of 1 to 8 carbons, chloro, bromo, carboxy, alkoxy radicals of 1to 8 carbons, alkoxycarbonyl radicals of 2 to 8 carbons or nitro.
 2. Aprocess as defined in claim 1 wherein the compound of structure A isused to initiate polymerization of ethylenically unsaturated monomers.3. A process as defined in claim 1 wherein the compound of structure Ais used to initiate curing of an elastomeric resin.
 4. A process asdefined in claim 1 wherein a compound of structure A is used to initiatemodification of a polymer selected from the group consisting ofpolypropylene and copolymers comprising more than 50% by weight ofpolypropylene.
 5. A process as defined in claim 1 wherein a compound ofstructure A is used to initiate crosslinking of olefin polymers.